Systems, methods, and catalysts for producing a crude product

ABSTRACT

Methods and systems for contacting of a crude feed with one or more catalysts to produce a total product that includes a crude product are described. The crude product is a liquid mixture at 25° C. and 0.101 MPa. The crude product has a nitrogen content of at most 90% of the nitrogen content of the crude feed. One or more other properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application60/670,136 filed on Apr. 11, 2005, herein incorporated by reference inits entirety.

FIELD OF THE INVENTION

The present invention generally relates to systems, methods, andcatalysts for treating crude feed. More particularly, certainembodiments described herein relate to systems, methods, and catalystsfor conversion of a crude feed to a total product, wherein the totalproduct includes a crude product that is a liquid mixture at 25° C. and0.101 MPa, and has one or more properties that are changed relative tothe respective property of the crude feed.

DESCRIPTION OF RELATED ART

Crudes that have one or more unsuitable properties that do not allow thecrudes to be economically transported, or processed using conventionalfacilities, are commonly referred to as “disadvantaged crudes”.

Disadvantaged crudes may include acidic components that contribute tothe total acid number (“TAN”) of the crude feed. Disadvantaged crudeswith a relatively high TAN may contribute to corrosion of metalcomponents during transporting and/or processing of the disadvantagedcrudes. Removal of acidic components from disadvantaged crudes mayinvolve chemically neutralizing acidic components with various bases.Alternately, corrosion-resistant metals may be used in transportationequipment and/or processing equipment. The use of corrosion-resistantmetal often involves significant expense, and thus, the use ofcorrosion-resistant metal in existing equipment may not be desirable.Another method to inhibit corrosion may involve addition of corrosioninhibitors to disadvantaged crudes before transporting and/or processingof the disadvantaged crudes. The use of corrosion inhibitors maynegatively affect equipment used to process the crudes and/or thequality of products produced from the crudes.

Disadvantaged crudes often contain relatively high levels of residue.Disadvantaged crudes having high levels of residue tend to be difficultand expensive to transport and/or process using conventional facilities.

Disadvantaged crudes often contain organically bound heteroatoms (forexample, sulfur, oxygen, and nitrogen). Organically bound heteroatomsmay, in some situations, have an adverse effect on catalysts used toprocess disadvantaged crudes.

Disadvantaged crudes may include relatively high amounts of metalcontaminants, for example, nickel, vanadium, and/or iron. Duringprocessing of such crudes, metal contaminants and/or compounds of metalcontaminants, may deposit on a surface of the catalyst or in the voidvolume of the catalyst. Such deposits may cause a decline in theactivity of the catalyst.

Disadvantaged crudes may have components that contribute coke and/or tothermal degradation of the disadvantaged crude. The coke and/orthermally degraded components may form and/or deposit on catalystsurfaces at a rapid rate during processing of disadvantaged crudes. Itmay be costly to regenerate the catalytic activity of a catalystcontaminated with coke and/or thermally degraded crude. Additionally,high temperatures used during regeneration of a catalyst may alsodiminish the activity of the catalyst and/or cause the catalyst todeteriorate.

Disadvantaged crudes may include metals (for example, calcium, potassiumand/or sodium) in metal salts of organic acids. Metals in metal salts oforganic acids are not typically separated from disadvantaged crudes byconventional production processing, for example, desalting and/or acidwashing.

Problems are often encountered in conventional catalytic processing ofcrudes when metals in metal salts of organic acids are present. Incontrast to nickel and vanadium, which typically deposit near theexternal surface of the catalyst, metals in metal salts of organic acidsmay deposit preferentially in void volumes between catalyst particles,particularly at the top of the catalyst bed. The deposit ofcontaminants, for example, metals in metal salts of organic acids, atthe top of the catalyst bed, generally results in an increase inpressure drop through the bed and may effectively plug the bed.Moreover, the metals in metal salts of organic acids may cause rapiddeactivation of catalysts.

Disadvantaged crudes may include organic oxygen compounds. Treatmentfacilities that process disadvantaged crudes with an oxygen content ofat least 0.002 grams of oxygen per gram of disadvantaged crude mayencounter problems during processing. Organic oxygen compounds, whenheated during processing, may form higher oxidation compounds (forexample, ketones and/or acids formed by oxidation of alcohols, and/oracids formed by oxidation of ethers) that are difficult to remove fromthe treated crude and/or may corrode/contaminate equipment duringprocessing and cause plugging in transportation lines.

Disadvantaged crudes may include hydrogen deficient hydrocarbons. Whenprocessing hydrogen deficient hydrocarbons, consistent quantities ofhydrogen generally need to be added, particularly if unsaturatedfragments resulting from cracking processes are produced. Hydrogenationduring processing, which typically involves the use of an activehydrogenation catalyst, may be needed to inhibit unsaturated fragmentsfrom forming coke. Hydrogen is costly to produce and/or costly totransport to treatment facilities.

Disadvantaged crudes also tend to exhibit instability during processingin conventional facilities. Crude instability tends to result in phaseseparation of components during processing and/or formation ofundesirable by-products (for example, hydrogen sulfide, water, andcarbon dioxide).

Conventional processes for treating disadvantaged crudes may reduce theamount of components that contribute to high viscosity, thermaldegradation of the disadvantaged crude, and/or coking. Removal of thesecomponents, however, may cause instability in the crude, thus causingseparation of the crude during transportation. During conventionalprocessing, components that contribute to high viscosity and/or cokingare typically removed when the crude is treated with a catalyst that hasa large pore size, a high surface area, and a low hydrotreatingactivity. The resulting crude may then be further treated to removeother unwanted components in the crude.

Some processes for improving the quality of crude include adding adiluent to disadvantaged crudes to lower the weight percent ofcomponents contributing to the disadvantaged properties. Adding diluent,however, generally increases costs of treating disadvantaged crudes dueto the costs of diluent and/or increased costs to handle thedisadvantaged crudes. Addition of diluent to a disadvantaged crude may,in some situations, decrease stability of such crude.

U.S. Pat. No. 6,547,957 to Sudhakar et al.; U.S. Pat. No. 6,277,269 toMyers et al.; U.S. Pat. No. 6,203,695 to Harle et al.; U.S. Pat. No.6,063,266 to Grande et al.; U.S. Pat. No. 5,928,502 to Bearden et al.;U.S. Pat. No. 5,914,030 to Bearden et al.; U.S. Pat. No. 5,897,769 toTrachte et al.; U.S. Pat. No. 5,744,025 to Boon et al.; U.S. Pat. No.4,212,729 to Hensley, Jr., and U.S. Pat. No. 4,048,060 to Riley; andU.S. Patent Application Publication No. US 2004/0106516 to Schulz etal., all of which are incorporated herein by reference, describe variousprocesses, systems, and catalysts for processing crudes. The processes,systems, and catalysts described in these patents, however, have limitedapplicability because of many of the technical problems set forth above.

In sum, disadvantaged crudes generally have undesirable properties (forexample, relatively high TAN, a tendency to become unstable duringtreatment, and/or a tendency to consume relatively large amounts ofhydrogen during treatment). Disadvantaged crudes may also includerelatively high amounts of undesirable components (for example,components that contribute to thermal degradation, residue, organicallybound heteroatoms, metal contaminants, metals in metal salts of organicacids, and/or organic oxygen compounds). Such properties and componentstend to cause problems in conventional transportation and/or treatmentfacilities, including increased corrosion, decreased catalyst life,process plugging, and/or increased usage of hydrogen during treatment.Thus, there is a significant economic and technical need for improvedsystems, methods, and/or catalysts for conversion of disadvantagedcrudes into crude products with more desirable properties. There is alsoa significant economic and technical need for systems, methods, and/orcatalysts that can change selected properties in a disadvantaged crudewhile minimizing changes to other properties in the disadvantaged crude.

SUMMARY OF THE INVENTION

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with one or morecatalysts to produce a total product that includes the crude product,wherein the crude product is a liquid mixture at 25° C. and 0.101 MPa;the crude feed has a micro-carbon residue (“MCR”) content of at least0.0001 grams per gram of crude feed; and at least one of the catalystsis a Column 6 metal catalyst that comprises: one or more metals fromColumn 6 of the Periodic Table and/or one or more compounds of one ormore metals from Column 6 of the Periodic Table; a pore sizedistribution with a median pore diameter of greater than 110 Å; and apore volume in which pores having a pore diameter of at least 350 Åprovide at most 10% of the pore volume, wherein pore volume and porediameter are as determined by ASTM Method D4282; and controllingcontacting conditions such that the crude product has a MCR content ofat most 90% of the MCR content of the crude feed, wherein MCR content isas determined by ASTM Method D4530.

In some embodiments, the invention also provides a catalyst, comprising:a support; and one or more metals from Column 6 of the Periodic Tableand/or one or more compounds of one or more metals from Column 6 of thePeriodic Table; wherein the catalyst has a pore size distribution with amedian pore diameter greater than 110 Å and a pore volume in which poreshaving a pore diameter of at least 350 Å provide at most 10% of the porevolume, wherein pore diameter and pore volume are as determined by ASTMMethod D4282.

In some embodiments, the invention also provides a method of making acatalyst, comprising: combining a support with a metal solutioncomprising one or more metals from Column 6 of the Periodic Table and/orone or more compounds of one or more metals from Column 6 of thePeriodic Table, wherein the support has an average pore diameter of atleast 90 Å and a pore volume in which pores having a pore diameter of atleast 350 Å provide at most 15% of the pore volume of the support,wherein pore diameter and pore volume are as determined by ASTM MethodD4282.

In some embodiments, the invention also provides a method of producing acrude product, comprising: contacting a crude feed with one or morecatalysts to produce a total product that includes the crude product,wherein the crude product is a liquid mixture at 25° C. and 0.101 MPa,the crude feed has a MCR content of at least 0.0001 grams per gram ofcrude feed, and at least one of the catalysts is a Columns 6-10 catalystthat has, per gram of catalyst, at least 0.3 grams of one or more metalsfrom Columns 6-10 of the Periodic Table and/or one or more compounds ofone or more metals from Columns 6-10 of the Periodic Table; and abinder; and controlling contacting conditions such that the crudeproduct has a MCR content of at most 90% of the MCR content of the crudefeed, wherein MCR content is as determined by ASTM Method D4530.

In some embodiments, the invention also provides a method of producing acrude product, comprising: contacting a crude feed with one or morecatalysts to produce a total product that includes the crude product,wherein the crude product is a liquid mixture at 25° C. and 0.101 MPa,the crude feed comprises one or more alkali metal salts of one or moreorganic acids, alkaline-earth metal salts of one or more organic acids,or mixtures thereof, the crude feed has, per gram of crude feed, a totalcontent of alkali metal and alkaline-earth metal in metal salts oforganic acids of at least 0.00001 grams, and at least one of thecatalysts is a Columns 5-10 metal catalyst that comprises: a support,the support comprising theta alumina; and one or more metals fromColumns 5-10 of the Periodic Table and/or one or more compounds of oneor more metals from Columns 5-10 of the Periodic Table; and controllingcontacting conditions such that the crude product has a total content ofalkali metal and alkaline-earth metal in metal salts of organic acids ofat most 90% of the content of alkali metal and alkaline-earth metal inmetal salts of organic acids in the crude feed, wherein content ofalkali metal and alkaline-earth metal in metal salts of organic acids isas determined by ASTM Method D11318.

In some embodiments, the invention also provides a method of producing acrude product, comprising: contacting a crude feed with one or morecatalysts to produce a total product that includes the crude product,wherein the crude product is a liquid mixture at 25° C. and 0.101 MPa;the crude feed has a nitrogen content of at least 0.0001 grams per gramof crude feed; and at least one of the catalysts is a Column 6 metalcatalyst that comprises: one or more metals from Column 6 of thePeriodic Table and/or one or more compounds of one or more metals fromColumn 6 of the Periodic Table; a pore size distribution with a medianpore diameter of greater than 110 Å; and a pore volume in which poreshaving a pore diameter of at least 350 Å provide at most 10% of the porevolume, wherein pore diameter and pore volume are as determined by ASTMMethod D4282; and controlling contacting conditions such that the crudeproduct has a nitrogen content of at most 90% of the nitrogen content ofthe crude feed, wherein nitrogen content is as determined by ASTM MethodD5762.

In some embodiments, the invention also provides a method of producing acrude product, comprising: contacting a crude feed with one or morecatalysts to produce a total product that includes the crude product,wherein the crude product is a liquid mixture at 25° C. and 0.101 MPa;the crude feed has a nitrogen content of at least 0.0001 grams per gramof crude feed; wherein at least one of the catalysts is a Column 6 metalcatalyst that is obtainable by heating a Column 6 metal catalystprecursor in the presence of one or more sulfur containing compounds ata temperature below about 500° C., wherein the Column 6 metal catalystprecursor comprises: one or more metals from Column 6 of the PeriodicTable and/or one or more compounds of one or more metals from Column 6of the Periodic Table; and a support; and controlling contactingconditions such that the crude product has a nitrogen content of at most90% of the nitrogen content of the crude feed, wherein nitrogen contentis as determined by ASTM Method D5762.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, the Column 6 metal catalyst: (a)in which pores having a pore diameter of at least 350 Å provide at most5%, at most 3%, at most 1%, or at most 0.5% of the pore volume; (b) hasa pore size distribution with a median pore diameter of at least 120 Å,at least 130 Å, at least 150 Å, at least 180 Å, at least 200 Å, at least250 Å, or at most 300 Å, wherein pore size distribution is as determinedby ASTM Method D4282; and/or (c) has a pore size distribution such thatat least 60% of the total number of pores in the pore size distributionare within about 45 Å, about 35 Å, or about 25 Å of the median porediameter of the pore size distribution.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, that the Column 6 metal catalyst:(a) has, per gram of catalyst, from about 0.0001 grams to about 0.3grams, about 0.005 grams to about 0.2 grams, or about 0.01 grams toabout 0.1 grams of one or more of the Column 6 metals and/or one or moreof the Column 6 metal compounds, calculated as total weight of Column 6metal; (b) comprises one or more metals from Columns 7-10 of thePeriodic Table and/or one or more compounds of one or more metals fromColumns 7-10 of the Periodic Table; and has, per gram of catalyst, fromabout 0.001 grams to about 0.1 grams or about 0.01 grams to about 0.05grams of one or more of the Columns 7-10 metals and/or one or more ofthe Columns 7-10 metal compounds, calculated as total weight of Columns7-10 metals; (c) comprises one or more metals from Column 10 of thePeriodic Table and/or one or more compounds of one or more metals fromColumn 10 of the Periodic Table; (d) comprises molybdenum and/ortungsten; (e) comprises nickel and/or cobalt; (f) comprises nickeland/or iron; (g) comprises one or more elements from Column 15 of thePeriodic Table and/or one or more compounds of one or more elements fromColumn 15 of the Periodic Table; and has, per gram of catalyst, fromabout 0.000001 grams to about 0.1 grams, about 0.00001 grams to about0.06 grams, about 0.00005 grams to about 0.03 grams, or about 0.0001grams to about 0.001 grams of one or more of the Column 15 elementsand/or one or more of the Column 15 element compounds, calculated astotal weight of Column 15 element; (h) comprises phosphorus; and/or (i)has, per gram of catalyst, at most 0.001 grams of one or more metalsfrom Column 5 of the Periodic Table and/or one or more compounds of oneor more metals from Column 5 of the Periodic Table, calculated as totalweight of Column 5 metal.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, that the Column 6 metal catalystor Column 6 metal solution has, per gram of catalyst or Column 6 metalsolution: (a) from about 0.01 grams to about 0.15 grams of molybdenumand/or one or more compounds of molybdenum, calculated as total weightof molybdenum; and from about 0.001 grams to about 0.05 grams of nickeland/or one or more compounds of nickel, calculated as total weight ofnickel; and (b) optionally, from about 0.001 grams to about 0.05 gramsof iron and/or one or more compounds of iron, calculated as total weightof iron; and (c) optionally, from about 0.0001 grams to about 0.05 gramsof phosphorus and/or one or more compounds of phosphorus, calculated astotal weight of phosphorus.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, that the Columns 5-10 metalcatalyst: (a) comprises molybdenum; (b) comprises tungsten; (c)comprises vanadium; (d) has, per gram of catalyst, from about 0.001grams to about 0.1 grams or about 0.01 grams to about 0.05 grams of oneor more metals from Columns 7-10 of the Periodic Table and/or one ormore compounds of one or more metals from Columns 7-10 of the PeriodicTable; (e) comprises one or more elements from Column 15 of the PeriodicTable and/or one or more compounds of one or more elements from Column15 of the Periodic Table; (f) comprises phosphorus; and/or (g) has apore size distribution with a median pore diameter of at least 180 Å, atleast 200 Å, at least 230 Å, at least 250 Å, or at least 300 Å.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, that the Column 6 metal catalystis a supported catalyst, in which the support has, per gram of support:(a) at least 0.8 grams, at least 0.9 grams, or at least 0.95 grams ofgamma alumina; (b) at most 0.1 grams, at most 0.08 grams, at most 0.06grams, at most 0.04 grams, or at most 0.02 grams of silica, or (c) atleast 0.3 grams or at least 0.5 grams of theta alumina.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, contacting the crude feed with oneor more catalysts in which at least one or more of the catalysts is aColumn 6 metal catalyst that is obtainable by combining a mixture withone or more of the Column 6 metals and/or one or more of the Column 6metal compounds, and the mixture comprises: one or more metals fromColumns 7-10 of the Periodic Table and/or one or more compounds of oneor more metals from Columns 7-10 of the Periodic Table; and a support.In some embodiments, in combination with one or more of the aboveembodiments, at least one of the Columns 7-10 metals comprises nickel,cobalt, iron, or mixtures thereof.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a crude feed that has: (a) fromabout 0.0001 grams to about 0.5 grams, about 0.005 grams to about 0.1grams, or about 0.01 grams to about 0.05 grams of MCR per gram of crudefeed; (b) from about 0.0001 grams to about 0.1 grams, about 0.001 gramsto about 0.05 grams, or about 0.005 grams to about 0.01 grams ofnitrogen per gram of crude feed; and/or (c) from about 0.00001 grams toabout 0.005 grams, about 0.00005 grams to about 0.05 grams, or about0.0001 grams to about 0.01 grams of alkali metal and alkaline-earthmetal in metal salts of organic acids per gram of crude feed.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a crude product that has: (a) aMCR content of at most 80%, at most 50%, at most 30%, or at most 10% ofthe MCR content of the crude feed; (b) a nitrogen content of at most80%, at most 50%, at most 30%, or at most 10% of the nitrogen content ofthe crude feed; (c) a total content of alkali metal, and alkaline-earthmetal in metal salts of organic acids in the crude product of at most80%, at most 50%, at most 30%, or at most 10% of the content of alkalimetal, and alkaline-earth metal, in metal salts of organic acids in thecrude feed; (d) a MCR content in a range from about 0.1% to about 75%,about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9%of the MCR content of the crude feed; (e) a nitrogen content in a rangefrom about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about25%, or about 2% to about 9% of the nitrogen content of the crude feed;(f) a total content of alkali metal and alkaline-earth metal in metalsalts of organic acids in the crude product in a range from about 0.1%to about 75%, from about 0.5% to about 45%, about 1% to about 25%, orabout 2% to about 9% of the content of alkali metal and alkaline-earthmetal in metal salts of organic acids in the crude feed; (g) from about0.00001 grams to about 0.1 grams, about 0.0001 grams to about 0.05grams, or about 0.001 grams to about 0.005 grams of MCR per gram ofcrude product; (h) from about 0.00001 grams to about 0.05 grams, about0.0001 grams to about 0.01 grams, or about 0.0005 grams to about 0.001grams of nitrogen per gram of crude product; (i) from about 1×10⁻⁷ gramsto about 5×10⁻⁵ grams, about 5×10⁻⁷ grams to about 1×10⁻⁵ grams, orabout 1×10⁻⁶ grams to about 5×10⁻⁶ grams of alkali metal andalkaline-earth metal in metal salts of organic acids per gram of crudeproduct; (j) a viscosity at 37.8° C. (100° F.) of at most 90%, at most80%, at most 70%, at most 50%, at most 30%, or at most 10% of theviscosity at 37.8° C. (100° F.) of the crude feed, wherein viscosity isas determined by ASTM Method D445; (k) a C₅ asphaltenes content of most90%, at most 80%, at most 70%, at most 50%, at most 30%, or at most 10%of the C₅ asphaltenes content of the crude feed, wherein C₅ asphaltenescontent is as determined by ASTM Method D2007; (1) a residue content ofat most 90%, at most 80%, at most 70%, at most 50%, at most 30%, or atmost 10% of the residue content of the crude feed, wherein residuecontent is as determined by ASTM Method D5307; and/or (m) a sulfurcontent of at most 90%, at most 80%, at most 70%, at most 50%, at most30%, or at most 10% of the sulfur content of the crude feed, whereinsulfur content is as determined by ASTM Method D4294.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, contacting the crude feed with oneor more catalysts and one or more additional catalysts, at least one ofthe catalysts is the Column 6 metal catalyst, and one or more of theadditional catalysts has a median pore diameter of at least 60 Å, atleast 90 Å, at least 110 Å, at least 180 Å, at least 200 Å, or at least250 Å; and the Column 6 metal catalyst is contacted with the crude feedprior to and/or after contact of the crude feed with at least one of theadditional catalysts.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, at least one of the catalysts isthe Columns 5-10 metal catalyst; and contacting the crude feed with anadditional catalyst having a median pore diameter of at least 60 Å, andthe additional catalyst is contacted with the crude feed subsequent tocontact of the crude feed with the Columns 5-10 metal catalyst.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, contacting the crude feed with oneor more catalysts to produce a total product in which, during contact, acrude feed/total product mixture has a P-value of at least 1.5.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, contacting in the presence of ahydrogen source.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, the contacting conditions whichcomprise: (a) a temperature within the range of about 50° C. to about500° C.; (b) a temperature of at most 430° C., at most 420° C., or atmost 410° C.; (c) a total pressure within a range of about 0.1 MPa toabout 20 MPa; (d) a total pressure of at most 18 MPa, at most 16 MPa, orat most 14 MPa; (e) a liquid hourly space velocity of at least 0.05 h⁻¹;and/or (f) a ratio of a gaseous hydrogen source to the crude feed in arange from about 0.1 Nm³/m³ to about 100,000 Nm³/m³.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method that comprises contactinga crude feed with one or more catalysts to produce a total product thatincludes a crude product, the method further comprising combining thecrude product with a crude that is the same as or different from thecrude feed to form a blend suitable for transporting.

In some embodiments, the invention provides, in combination with one ormore of the above embodiments, a method of making a catalyst thatincludes combining a support with a Column 6 metal solution: (a) thathas a pH of up to about 3; (b) that has a pH in a range from about 1 toabout 3; (c) in which an amount of Column 6 metal in the metal solutionis selected such that the catalyst has, per gram of catalyst, from about0.0001 grams to about 0.3 grams, about 0.005 grams to about 0.2 grams,or about 0.01 grams to about 0.1 grams of one or more of the Column 6metals and/or one or more of the Column 6 metal compounds, calculated astotal weight of Column 6 metal; (d) that comprises one or more metalsfrom Columns 7-10 of the Periodic Table and/or one or more compounds ofone or more metals from Columns 7-10 of the Periodic Table; and where anamount of Columns 7-10 metals is selected such that the catalyst has,per gram of catalyst, from about 0.001 grams to about 0.1 grams or about0.01 grams to about 0.05 grams of one or more of the Columns 7-10 metalsand/or one or more of the Columns 7-10 metal compounds, calculated astotal weight of Columns 7-10 metals; (e) that comprises one or moremetals from Column 10 of the Periodic Table and/or one or more compoundsof one or more metals from Column 10 of the Periodic Table; (f) thatcomprises molybdenum and/or tungsten; (g) that comprises nickel and/orcobalt; (h) that comprises nickel and iron; (i) that comprises one ormore elements from Column 15 of the Periodic Table and/or one or morecompounds of one or more elements from Column 15 of the Periodic Table;and where an amount of Columns 15 elements is selected such that thecatalyst has, per gram of catalyst, from about 0.000001 grams to about0.1 grams, about 0.00001 grams to about 0.06 grams, about 0.00005 gramsto about 0.03 grams, or about 0.0001 grams to about 0.001 grams of oneor more of the Column 15 elements and/or one or more of the Column 15element compounds, calculated as total weight of Column 15 element; (j)that comprises phosphorus; (k) that comprises one or more mineral acids;(l) that comprises one or more organic acids; (m) that compriseshydrogen peroxide; and/or (n) that comprises an amine.

In some embodiments, the invention provides, in combination with one ormore of the above embodiments, a method of making a catalyst thatincludes: heat-treating the supported metal at a temperature in a rangefrom about 40° C. to about 400° C., about 60° C. to about 300° C., orabout 100° C. to about 200° C.; and optionally further heat-treating thesupported metal at a temperature of at least 400° C.

In some embodiments, the invention provides, in combination with one ormore of the above embodiments, a Columns 6-10 metal catalyst: (a) thatcomprises one or more metals from Column 6 of the Periodic Table and/orone or more compounds of one or more metals from Column 6 of thePeriodic Table; (b) that comprises one or more metals from Columns 7-10of the Periodic Table and/or one or more compounds of one or more metalsfrom Columns 7-10 of the Periodic Table; (c) that comprises molybdenumand/or tungsten; (d) that comprises nickel and/or cobalt; (e) in whichthe binder comprises silica, alumina, silica/alumina, titanium oxide,zirconium oxide, or mixtures thereof; and/or (f) that is amorphous.

In further embodiments, features from specific embodiments may becombined with features from other embodiments. For example, featuresfrom one embodiment may be combined with features from any of the otherembodiments.

In further embodiments, crude products are obtainable by any of themethods and systems described herein.

In further embodiments, additional features may be added to the specificembodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of the present invention will become apparent to thoseskilled in the art with the benefit of the following detaileddescription and upon reference to the accompanying drawings in which:

FIG. 1 is a schematic of an embodiment of a contacting system.

FIGS. 2A and 2B are schematics of embodiments of contacting systems thatinclude two contacting zones.

FIGS. 3A and 3B are schematics of embodiments of contacting systems thatinclude three contacting zones.

FIG. 4 is a schematic of an embodiment of a separation zone incombination with a contacting system.

FIG. 5 is a schematic of an embodiment of a blending zone in combinationwith a contacting system.

FIG. 6 is a schematic of an embodiment of a combination of a separationzone, a contacting system, and a blending zone.

While the invention is susceptible to various modifications andalternative forms, specific embodiments thereof are shown by way ofexample in the drawings. The drawings may not be to scale. It should beunderstood that the drawings and detailed description thereto are notintended to limit the invention to the particular form disclosed, but onthe contrary, the intention is to cover all modifications, equivalentsand alternatives falling within the spirit and scope of the presentinvention as defined by the appended claims.

DETAILED DESCRIPTION

The above problems may be addressed using systems, methods, andcatalysts described herein. For example, the crude product havingreduced MCR content and/or a reduced nitrogen content relative to theMCR content and/or the nitrogen content of the crude feed is produced bycontacting the crude feed with the catalyst that has a pore sizedistribution with a median pore diameter of greater than 110 Å, and apore volume in which pores having a pore diameter of at least 350 Åprovide at most 10% of the pore volume. Crude product having reducednitrogen content relative to the nitrogen content of the crude feed isproduced by contacting the crude feed with the uncalcined catalyst.Crude product having reduced content of metals in metal salts of organicacids relative to the content of metals in metal salts of organic acidsof the crude feed is produced by contacting the crude feed with thecatalyst that includes Columns 5-10 metal(s) and theta alumina. Crudeproduct having reduced MCR content relative to the MCR content of thecrude feed is produced by contacting the crude feed with the bulk metalcatalyst.

U.S. application Ser. Nos. 11/014,335; 11/013,553; 11/014,386;11/013,554; 11/013,629; 11/014,318; 11/013,576; 11/013,835; 11/014,362;11/014,011; 11/013,747; 11/013,918; 11/014,275; 11/014,060; 11/014,272;11/014,380; 11/014,005; 11/013,998; 11/014,406; 11/014,365; 11/013,545;11/014,132; 11/014,363; 11/014,251; 11/013,632; 11/014,009; 11/014,297;11/014,004; 11/013,999; 11/014,281; 11/013,995; 11/013,904, 11/013,952;11/014,299; 11/014,381; 11/014,346; 11/014,028; 11/013,826; and11/013,622 also discuss systems, methods, and catalysts that address theabove problems, albeit with respect to crude feeds that may differ insome respects from the crude feeds treated in accordance with theinventions described herein.

Certain embodiments of the inventions are described herein in moredetail. Terms used herein are defined as follows.

“ASTM” refers to American Standard Testing and Materials.

“API gravity” refers to API gravity at 15.5° C. (60° F.). API gravity isas determined by ASTM Method D6822.

Atomic hydrogen percentage and atomic carbon percentage of the crudefeed and the crude product are as determined by ASTM Method D5291.

Boiling range distributions for the crude feed, the total product,and/or the crude product are as determined by ASTM Method D5307 unlessotherwise mentioned.

“Binder” refers to a substrate that combines smaller particles togetherto form larger substances (for example, blocks or pellets).

“Bulk metal catalyst” refers to a catalyst that includes at least onemetal, and does not require a carrier or a support.

“C₅ asphaltenes” refers to asphaltenes that are insoluble in pentane. C₅asphaltenes content is as determined by ASTM Method D2007.

“Column X metal(s)” refers to one or more metals of Column X of thePeriodic Table and/or one or more compounds of one or more metals ofColumn X of the Periodic Table, in which X corresponds to a columnnumber (for example, 1-12) of the Periodic Table. For example, “Column 6metal(s)” refers to one or more metals from Column 6 of the PeriodicTable and/or one or more compounds of one or more metals from Column 6of the Periodic Table.

“Column X element(s)” refers to one or more elements of Column X of thePeriodic Table, and/or one or more compounds of one or more elements ofColumn X of the Periodic Table, in which X corresponds to a columnnumber (for example, 13-18) of the Periodic Table. For example, “Column15 element(s)” refers to one or more elements from Column 15 of thePeriodic Table and/or one or more compounds of one or more elements fromColumn 15 of the Periodic Table.

In the scope of this application, weight of a metal from the PeriodicTable, weight of a compound of a metal from the Periodic Table, weightof an element from the Periodic Table, or weight of a compound of anelement from the Periodic Table is calculated as the weight of metal orthe weight of element. For example, if 0.1 grams of MoO₃ is used pergram of catalyst, the calculated weight of the molybdenum metal in thecatalyst is 0.067 grams per gram of catalyst.

“Content” refers to the weight of a component in a substrate (forexample, a crude feed, a total product, or a crude product) expressed asweight fraction or weight percentage based on the total weight of thesubstrate. “Wtppm” refers to parts per million by weight.

“Crude feed/total product mixture” refers to the mixture that contactsthe catalyst during processing.

“Distillate” refers to hydrocarbons with a boiling range distributionbetween 204° C. (400° F.) and 343° C. (650° F.) at 0.101 MPa. Distillatecontent is as determined by ASTM Method D5307.

“Heteroatoms” refers to oxygen, nitrogen, and/or sulfur contained in themolecular structure of a hydrocarbon. Heteroatoms content is asdetermined by ASTM Methods E385 for oxygen, D5762 for total nitrogen,and D4294 for sulfur. “Total basic nitrogen” refers to nitrogencompounds that have a pKa of less than 40. Basic nitrogen (“bn”) is asdetermined by ASTM Method D2896.

“Hydrogen source” refers to hydrogen, and/or a compound and/or compoundsthat when in the presence of a crude feed and a catalyst react toprovide hydrogen to compound(s) in the crude feed. A hydrogen source mayinclude, but is not limited to, hydrocarbons (for example, C₁ to C₄hydrocarbons such as methane, ethane, propane, butane), water, ormixtures thereof. A mass balance may be conducted to assess the netamount of hydrogen provided to the compound(s) in the crude feed.

“Flat plate crush strength” refers to compressive force needed to crusha catalyst. Flat plate crush strength is as determined by ASTM MethodD4179.

“LHSV” refers to a volumetric liquid feed rate per total volume ofcatalyst, and is expressed in hours (h⁻¹). Total volume of catalyst iscalculated by summation of all catalyst volumes in the contacting zones,as described herein.

“Liquid mixture” refers to a composition that includes one or morecompounds that are liquid at standard temperature and pressure (25° C.,0.101 MPa, hereinafter referred to as “STP”), or a composition thatincludes a combination of one of more compounds that are liquid at STPwith one or more compounds that are solids at STP.

“Periodic Table” refers to the Periodic Table as specified by theInternational Union of Pure and Applied Chemistry (IUPAC), November2003.

“Metals in metal salts of organic acids” refer to alkali metals,alkaline-earth metals, zinc, arsenic, chromium, or combinations thereof.A content of metals in metal salts of organic acids is as determined byASTM Method D1318.

“MCR” content refers to a quantity of carbon residue remaining afterevaporation and pyrolysis of a substrate. MCR content is as determinedby ASTM Method D4530.

“Naphtha” refers to hydrocarbon components with a boiling rangedistribution between 38° C. (100° F.) and 200° C. (392° F.) at 0.101MPa. Naphtha content is as determined by ASTM Method D5307.

“Ni/V/Fe” refers to nickel, vanadium, iron, or combinations thereof.

“Ni/V/Fe content” refers to the content of nickel, vanadium, iron, orcombinations thereof. The Ni/V/Fe content is as determined by ASTMMethod D5708.

“Nm³/m³” refers to normal cubic meters of gas per cubic meter of crudefeed.

“Non-carboxylic containing organic oxygen compounds” refers to organicoxygen compounds that do not have a carboxylic (—CO₂—) group.Non-carboxylic containing organic oxygen compounds include, but are notlimited to, ethers, cyclic ethers, alcohols, aromatic alcohols, ketones,aldehydes, or combinations thereof, which do not have a carboxylicgroup.

“Non-condensable gas” refers to components and/or mixtures of componentsthat are gases at STP.

“P (peptization) value” or “P-value” refers to a numeral value, whichrepresents the flocculation tendency of asphaltenes in the crude feed.Determination of the P-value is described by J. J. Heithaus in“Measurement and Significance of Asphaltene Peptization”, Journal ofInstitute of Petroleum, Vol. 48, Number 458, February 1962, pp. 45-53.

“Pore diameter”, “average pore diameter”, “median pore diameter”, and“pore volume” refer to pore diameter, average pore diameter, median porediameter, and pore volume, as determined by ASTM Method D4284 (mercuryporosimetry at a contact angle equal to 140°). A micromeritics® A9220instrument (Micromeritics Inc., Norcross, Ga., U.S.A.) may be used todetermine these values. Pore volume includes the volume of all pores inthe catalyst. Median pore diameter refers to the pore diameter where 50%of the total number of pores have a pore diameter above the median porediameter and 50% of the total number of pores have a pore diameter belowthe median pore diameter. Average pore diameter, expressed in Angstromunits (A), is determined using the following equation:Average pore diameter=(40,000×total pore volume in cm³/g)/(surface areain m²/g).

“Residue” refers to components that have a boiling range distributionabove 538° C. (1000° F.), as determined by ASTM Method D5307.

“SCFB” refers to standard cubic feet of gas per barrel of crude feed.

“Surface area” of a catalyst is as determined by ASTM Method D3663.

“TAN” refers to a total acid number expressed as milligrams (“mg”) ofKOH per gram (“g”) of sample. TAN is as determined by ASTM Method D664.

“VGO” refers to hydrocarbons with a boiling range distribution between343° C. (650° F.) and 538° C. (1000° F.) at 0.101 MPa. VGO content is asdetermined by ASTM Method D5307.

“Viscosity” refers to kinematic viscosity at 37.8° C. (100° F.).Viscosity is as determined using ASTM Method D445.

All referenced methods are incorporated herein by reference. In thecontext of this application, it is to be understood that if the valueobtained for a property of the substrate tested is outside of limits ofthe test method, the test method may be modified and/or recalibrated totest for such property.

Crudes may be produced and/or retorted from hydrocarbon containingformations and then stabilized. Crudes are generally solid, semi-solid,and/or liquid. Crudes may include crude oil. Stabilization may include,but is not limited to, removal of non-condensable gases, water, salts,solids, or combinations thereof from the crude to form a stabilizedcrude. Such stabilization may often occur at, or proximate to, theproduction and/or retorting site.

Stabilized crudes include crudes that have not been distilled and/orfractionally distilled in a treatment facility to produce multiplecomponents with specific boiling range distributions (for example,naphtha, distillates, VGO, and/or lubricating oils). Distillationincludes, but is not limited to, atmospheric distillation methods and/orvacuum distillation methods. Undistilled and/or unfractionatedstabilized crudes may include components that have a carbon number above4 in quantities of at least 0.5 grams of such components per gram ofcrude. Stabilized crudes also include crudes from a surface retortingprocesses. For example, Canadian tar sands may be mined, and thentreated in a surface retorting process. The crude produced from suchsurface retorting may be a stabilized crude. Examples of stabilizedcrudes include whole crudes, topped crudes, desalted crudes, desaltedtopped crudes, retorted crudes, or mixtures thereof. “Topped” refers toa crude that has been treated such that at least some of the componentsthat have a boiling point below 35° C. at 0.101 MPa (about 95° F. at 1atm) have been removed. Typically, topped crudes will have a content ofat most 0.1 grams, at most 0.05 grams, or at most 0.02 grams of suchcomponents per gram of the topped crude.

Some stabilized crudes have properties that allow the stabilized crudesto be transported to conventional treatment facilities by transportationcarriers (for example, pipelines, trucks, or ships). Other crudes haveone or more unsuitable properties that render them disadvantaged.Disadvantaged crudes may be unacceptable to a transportation carrierand/or a treatment facility, thus imparting a low economic value to thedisadvantaged crude. The economic value may be such that a reservoirthat includes the disadvantaged crude is deemed too costly to produce,transport, and/or treat.

Properties of disadvantaged crudes may include, but are not limited to:a) TAN of at least 0.1, or at least 0.3; b) viscosity of at least 10cSt; c) API gravity of at most 19; d) a total NiN/Fe content of at least0.00002 grams or at least 0.0001 grams of Ni/V/Fe per gram ofdisadvantaged crude; e) a total heteroatoms content of at least 0.005grams of heteroatoms per gram of disadvantaged crude; f) a residuecontent of at least 0.01 grams of residue per gram of disadvantagedcrude; g) a C₅ asphaltenes content of at least 0.04 grams of C₅asphaltenes per gram of disadvantaged crude; h) a MCR content of atleast 0.0001 grams of MCR per gram of disadvantaged crude; i) a contentof metals in metal salts of organic acids of at least 0.00001 grams ofmetals per gram of disadvantaged crude; or j) combinations thereof. Insome embodiments, disadvantaged crudes includes, per gram ofdisadvantaged crude, at least 0.2 grams of residue, at least 0.3 gramsof residue, at least 0.5 grams of residue, or at least 0.9 grams ofresidue. In some embodiments, disadvantaged crudes have a TAN in a rangefrom about 0.1 to about 20, about 0.3 to about 10, or about 0.4 to about5. In certain embodiments, disadvantaged crudes, per gram ofdisadvantaged crude, have a sulfur content of at least 0.005, at least0.01, or at least 0.02 grams.

In certain embodiments, disadvantaged crudes have, per gram ofdisadvantaged crude, an MCR content of at least 0.0001 grams, at least0.001 grams, at least 0.003 grams, at least 0.005 grams, at least 0.01grams, at least 0.1 grams, or at least 0.5 grams. Disadvantaged crudesmay have, per gram of disadvantaged crude, an MCR content in a rangefrom about 0.0001 grams to about 0.5 grams, from about 0.005 grams toabout 0.1 grams, or from about 0.01 grams to about 0.05 grams.

In some embodiments, disadvantaged crudes have, per gram ofdisadvantaged crude, a nitrogen content of at least 0.0001 grams, atleast 0.001 grams, at least 0.01 grams, at least 0.05 grams, or at least0.1 grams. Disadvantaged crudes may have, per gram of disadvantagedcrude, a nitrogen content in a range from about 0.0001 grams to about0.1 grams, from about 0.001 grams to about 0.05 grams, or from about0.005 grams to about 0.01 grams.

In certain embodiments, disadvantaged crudes have at least 0.00001grams, at least 0.0001 grams, at least 0.001 grams, or at least 0.01grams, of alkali and alkaline earth metals in metal salts of organicacids. Disadvantaged crudes may have a content of metals in metal saltsof organic acids in a range from about 0.00001 grams to about 0.003grams, about 0.00005 grams to about 0.005 grams, or about 0.0001 gramsto about 0.01 grams of alkali metal and alkaline-earth metal in metalsalts of organic acids.

In some embodiments, disadvantaged crudes have properties including, butnot limited to: a) TAN of at least 0.5; b) an oxygen content of at least0.005 grams of oxygen per gram of crude feed; c) a C₅ aspnaltenescontent of at least 0.04 grams of C₅ asphaltenes per gram of crude feed;d) a higher than desired viscosity (for example, greater than or equalto 10 cSt for a crude feed with API gravity of at least 10; e) a contentof metals in metal salts of organic acids of at least 0.00001 grams ofalkali and alkaline earth metals per gram of crude; or f) combinationsthereof.

Disadvantaged crudes may include, per gram of disadvantaged crude: atleast 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution between about 95° C. andabout 200° C. at 0.101 MPa; at least 0.001 grams, at least 0.005 grams,or at least 0.01 grams of hydrocarbons with a boiling range distributionbetween about 200° C. and about 300° C. at 0.101 MPa; at least 0.001grams, at least 0.005 grams, or at least 0.01 grams of hydrocarbons witha boiling range distribution between about 300° C. and about 400° C. at0.101 MPa; and at least 0.001 grams, at least 0.005 grams, or at least0.01 grams of hydrocarbons with a boiling range distribution betweenabout 400° C. and 650° C. at 0.101 MPa.

Disadvantaged crudes may include, per gram of disadvantaged crude: atleast 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution of at most 100° C. at0.101 MPa; at least 0.001 grams, at least 0.005 grams, or at least 0.01grams of hydrocarbons with a boiling range distribution between about100° C. and about 200° C. at 0.101 MPa; at least 0.001 grams, at least0.005 grams, or at least 0.01 grams of hydrocarbons with a boiling rangedistribution between about 200° C. and about 300° C. at 0.101 MPa; atleast 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution between about 300° C. andabout 400° C. at 0.101 MPa; and at least 0.001 grams, at least 0.005grams, or at least 0.01 grams of hydrocarbons with a boiling rangedistribution between about 400° C. and 650° C. at 0.101 MPa.

Some disadvantaged crudes may include, per gram of disadvantaged crude,at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution of at most 100° C. at0.101 MPa, in addition to higher boiling components. Typically, thedisadvantaged crude has, per gram of disadvantaged crude, a content ofsuch hydrocarbons of at most 0.2 grams or at most 0.1 grams.

Some disadvantaged crudes may include, per gram of disadvantaged crude,at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution below 200° C. at 0.101MPa.

In certain embodiments, disadvantaged crudes include, per gram ofdisadvantaged crude, up to 0.9 grams, or up to 0.99 grams ofhydrocarbons with a boiling range distribution above 300° C. In certainembodiments, disadvantaged crudes also include, per gram ofdisadvantaged crude, at least 0.001 grams of hydrocarbons with a boilingrange distribution above 650° C. In certain embodiments, disadvantagedcrudes include, per gram of disadvantaged crude, up to about 0.9 grams,or up to about 0.99 grams of hydrocarbons with a boiling rangedistribution between about 300° C. and about 1000° C.

Examples of disadvantaged crudes that might be treated using theprocesses described herein include, but are not limited to, crudes fromof the following regions of the world: U.S. Gulf Coast, southernCalifornia, north slope of Alaska, Canada tar sands, Canadian Albertaregion, Mexico Bay of Campeche, Argentinean San Jorge basin, BrazilianSantos and Campos basins, Egyptian Gulf of Suez, Chad, United KingdomNorth Sea, Angola Offshore, China Bohai Bay, China Karamay, Iraq Zagros,Kazakhstan Caspian, Nigeria Offshore, Madagascar northwest, Oman,Netherlands Schoonebek, Venezuelan Zulia, Malaysia, and IndonesiaSumatra. Treatment of disadvantaged crudes may enhance the properties ofthe disadvantaged crudes such that the crudes are acceptable fortransportation and/or treatment. A crude and/or disadvantaged crude thatis to be treated herein is referred to as “crude feed”. The crude feedmay be topped, as described herein. The crude feed may be obtainable by,but is not limited to, methods as described herein. The crude productresulting from treatment of the crude feed, as described herein, isgenerally suitable for transporting and/or treatment. Properties of thecrude product produced as described herein are closer to thecorresponding properties of West Texas Intermediate crude than the crudefeed, or closer to the corresponding properties of Brent crude, than thecrude feed, thereby enhancing the economic value of the crude feed. Suchcrude product may be refined with less pre-treatment than other crudeproducts from disadvantaged crude feeds, or no pre-treatment, therebyenhancing refining efficiencies. Pre-treatment may includedesulfurization, demetallization and/or atmospheric distillation toremove impurities.

Treatment of a crude feed in accordance with inventions described hereinmay include contacting the crude feed with the catalyst(s) in acontacting zone and/or combinations of two or more contacting zones. Ina contacting zone, at least one property of a crude feed may be changedby contact of the crude feed with one or more catalysts relative to thesame property of the crude feed. In some embodiments, contacting isperformed in the presence of a hydrogen source. In some embodiments, thehydrogen source is one or more hydrocarbons that under certaincontacting conditions react to provide relatively small amounts ofhydrogen to compound(s) in the crude feed.

FIG. 1 is a schematic of contacting system 100 that includes an upstreamcontacting zone 102. The crude feed enters upstream contacting zone 102via crude feed conduit 104. A contacting zone may be a reactor, aportion of a reactor, multiple portions of a reactor, or combinationsthereof. Examples of a contacting zone include a stacked bed reactor, afixed bed reactor, an ebullating bed reactor, a continuously stirredtank reactor (“CSTR”), a fluidized bed reactor, a spray reactor, and aliquid/liquid contactor. In certain embodiments, the contacting systemis on or coupled to an offshore facility. Contact of the crude feed withthe catalyst(s) in contacting system 100 may be a continuous process ora batch process.

The contacting zone may include one or more catalysts (for example, twocatalysts). In some embodiments, contact of the crude feed with a firstcatalyst of the two catalysts may reduce metals in metal salts oforganic acids of the crude feed. Subsequent contact of the crude feedhaving reduced metal salts with the second catalyst may decrease MCRcontent and/or heteroatoms content. In other embodiments, TAN,viscosity, Ni/V/Fe content, heteroatoms content, residue content, APIgravity, or combinations of these properties of the crude product changeby at least 10% relative to the same properties of the crude feed aftercontact of the crude feed with one or more catalysts.

In certain embodiments, a volume of catalyst in the contacting zone isin a range from about 10% to about 60 vol %, about 20% to about 50 vol%, or about 30% to about 40 vol % of a total volume of crude feed in thecontacting zone. In some embodiments, a slurry of catalyst and crudefeed may include from about 0.001 grams to about 10 grams, about 0.005grams to about 5 grams, or about 0.01 grams to about 3 grams of catalystper 100 grams of crude feed in the contacting zone.

Contacting conditions in the contacting zone may include, but are notlimited to, temperature, pressure, hydrogen source flow, crude feedflow, or combinations thereof. Contacting conditions in some embodimentsare controlled to produce a crude product with specific properties.Temperature in the contacting zone may range from about 50° C. to about500° C., about 60° C. to about 440° C., about 70° C. to about 430° C.,or about 80° C. to about 420° C. Pressure in a contacting zone may rangefrom about 0.1 MPa to about 20 MPa, about 1 MPa to about 12 MPa, about 4MPa to about 10 MPa, or about 6 MPa to about 8 MPa. LHSV of the crudefeed will generally range from about 0.05 h⁻¹ to about 30 h⁻¹, about 0.5h⁻¹ to about 25 h⁻¹, about 1 h⁻¹ to about 20 h⁻¹, about 1.5 h⁻¹, toabout 15 h⁻¹, or about 2 h⁻¹ to about 10 h⁻¹. In some embodiments, LHSVis at least 5 h⁻¹, at least 11 h⁻¹, at least 15 h⁻¹, or at least 20 h⁻¹.In some embodiments, the total pressure is at most 18 MPa, at most 16MPa, at most 14 MPa, at most 12 MPa, at most 10 MPa, or at most 8 MPa.In certain embodiments, the temperature is at most 430° C., at most 420°C., at most 410° C., or at most 400° C.

In embodiments in which the hydrogen source is supplied as a gas (forexample, hydrogen gas), a ratio of the gaseous hydrogen source to thecrude feed typically ranges from about 0.1 Nm³/m³ to about 100,000Nm³/m³, about 0.5 Nm³/m³ to about 10,000 Nm³/m³, about 1 Nm³/m³ to about8,000 Nm³/m³, about 2 Nm³/m³ to about 5,000 Nm³/m³, about 5 Nm³/m³ toabout 3,000 Nm³/m³, or about 10 Nm³/m³ to about 800 Nm³/m³ contactedwith the catalyst(s). The hydrogen source, in some embodiments, iscombined with carrier gas(es) and recirculated through the contactingzone. Carrier gas may be, for example, nitrogen, helium, and/or argon.The carrier gas may facilitate flow of the crude feed and/or flow of thehydrogen source in the contacting zone(s). The carrier gas may alsoenhance mixing in the contacting zone(s). In some embodiments, ahydrogen source (for example, hydrogen, methane or ethane) may be usedas a carrier gas and recirculated through the contacting zone.

The hydrogen source may enter upstream contacting zone 102 co-currentlywith the crude feed in crude feed conduit 104 or separately via gasconduit 106. In upstream contacting zone 102, contact of the crude feedwith a catalyst produces a total product that includes a crude product,and, in some embodiments, gas. In some embodiments, a carrier gas iscombined with the crude feed and/or the hydrogen source in conduit 106.The total product may exit upstream contacting zone 102 and enterdownstream separation zone 108 via total product conduit 110.

In downstream separation zone 108, the crude product and gas may beseparated from the total product using generally known separationtechniques, for example, gas-liquid separation. The crude product mayexit downstream separation zone 108 via crude product conduit 112, andthen be transported to transportation carriers, pipelines, storagevessels, refineries, other processing zones, or a combination thereof.The gas may include gas formed during processing (for example, hydrogensulfide, carbon dioxide, and/or carbon monoxide), excess gaseoushydrogen source, and/or carrier gas. The excess gas may be recycled tocontacting system 100, purified, transported to other processing zones,storage vessels, or combinations thereof.

In some embodiments, contacting the crude feed with the catalyst(s) toproduce a total product is performed in two or more contacting zones.The total product may be separated to form the crude product andgas(es).

FIGS. 2-3 are schematics of embodiments of contacting system 100 thatincludes two or three contacting zones. In FIGS. 2A and 2B, contactingsystem 100 includes upstream contacting zone 102 and downstreamcontacting zone 114. FIGS. 3A and 3B include contacting zones 102, 114,116. In FIGS. 2A and 3A, contacting zones 102, 114, 116 are depicted asseparate contacting zones in one reactor. The crude feed enters upstreamcontacting zone 102 via crude feed conduit 104.

In some embodiments, the carrier gas is combined with the hydrogensource in gas conduit 106 and is introduced into the contacting zones asa mixture. In certain embodiments, as shown in FIGS. 1, 3A, and 3B, thehydrogen source and/or the carrier gas may enter the one or morecontacting zones with the crude feed separately via gas conduit 106and/or in a direction counter to the flow of the crude feed via, forexample, gas conduit 106′. Addition of the hydrogen source and/or thecarrier gas counter to the flow of the crude feed may enhance mixingand/or contact of the crude feed with the catalyst.

Contact of the crude feed with catalyst(s) in upstream contacting zone102 forms a feed stream. The feed stream flows from upstream contactingzone 102 to downstream contacting zone 114. In FIGS. 3A and 3B, the feedstream flows from downstream contacting zone 114 to additionaldownstream contacting zone 116.

Contacting zones 102, 114, 116 may include one or more catalysts. Asshown in FIG. 2B, the feed stream exits upstream contacting zone 102 viafeed stream conduit 118 and enters downstream contacting zone 114. Asshown in FIG. 3B, the feed stream exits downstream contacting zone 114via conduit 118 and enters additional downstream contacting zone 116.

The feed stream may be contacted with additional catalyst(s) indownstream contacting zone 114 and/or additional downstream contactingzone 116 to form the total product. The total product exits downstreamcontacting zone 114 and/or additional downstream contacting zone 116 andenters downstream separation zone 108 via total product conduit 110. Thecrude product and/or gas is (are) separated from the total product. Thecrude product exits downstream separation zone 108 via crude productconduit 112.

FIG. 4 is a schematic of an embodiment of a separation zone upstream ofcontacting system 100. The disadvantaged crude (either topped oruntopped) enters upstream separation zone 120 via crude conduit 122. Inupstream separation zone 120, at least a portion of the disadvantagedcrude is separated using techniques known in the art (for example,sparging, membrane separation, pressure reduction, filtering, orcombinations thereof) to produce the crude feed. For example, water maybe at least partially separated from the disadvantaged crude in upstreamseparation zone 120. In another example, components that have a boilingrange distribution below 95° C. or below 100° C. may be at leastpartially separated from the disadvantaged crude in upstream separationzone 120 to produce the crude feed. In some embodiments, at least aportion of naphtha and compounds more volatile than naphtha areseparated from the disadvantaged crude. In some embodiments, at least aportion of the separated components exit upstream separation zone 120via conduit 124.

The crude feed obtained from upstream separation zone 120, in someembodiments, includes a mixture of components with a boiling rangedistribution of at least 100° C. or, in some embodiments, a boilingrange distribution of at least 120° C. Typically, the separated crudefeed includes a mixture of components with a boiling range distributionbetween about 100° C. to about 1000° C., about 120° C. to about 900° C.,or about 200° C. to about 800° C. At least a portion of the crude feedexits upstream separation zone 120 and enters contacting system 100(see, for example, the contacting zones in FIGS. 1-3) via additionalcrude feed conduit 126 to be further processed to form a crude product.In some embodiments, upstream separation zone 120 may be positionedupstream or downstream of a desalting unit. In certain embodiments,upstream separation zone 120 may be positioned downstream of a retortingprocess for bitumen, oil shale, and/or tar sands. After processing, thecrude product exits contacting system 100 via crude product conduit 112.

In some embodiments, the crude product is blended with a crude that isthe same as or different from the crude feed. For example, the crudeproduct may be combined with a crude having a different viscositythereby resulting in a blended product having a viscosity that isbetween the viscosity of the crude product and the viscosity of thecrude. In another example, the crude product may be blended with crudehaving a TAN and/or MCR content that is different, thereby producing aproduct that has a TAN and/or MCR content that is between the TAN and/orMCR content of the crude product and the crude. The blended product maybe suitable for transportation and/or treatment.

As shown in FIG. 5, in certain embodiments, crude feed enters contactingsystem 100 via crude feed conduit 104, and at least a portion of thecrude product exits contacting system 100 via conduit 128 and isintroduced into blending zone 130. In blending zone 130, at least aportion of the crude product is combined with one or more processstreams (for example, a hydrocarbon stream such as naphtha produced fromseparation of one or more crude feeds), a crude, a crude feed, ormixtures thereof, to produce a blended product. The process streams,crude feed, crude, or mixtures thereof are introduced directly intoblending zone 130 or upstream of such blending zone via stream conduit132. A mixing system may be located in or near blending zone 130. Theblended product may meet product specifications designated by refineriesand/or transportation carriers. Product specifications include, but arenot limited to, a range of or a limit of API gravity, TAN, viscosity, orcombinations thereof. The blended product exits blending zone 130 viablend conduit 134 to be transported or processed.

In FIG. 6, the disadvantaged crude enters upstream separation zone 120through crude conduit 122, and the disadvantaged crude is separated aspreviously described to form the crude feed. The crude feed then enterscontacting system 100 through additional crude feed conduit 126. Atleast some components from the disadvantaged crude exit separation zone120 via conduit 124. At least a portion of the crude product exitscontacting system 100 and enters blending zone 130 through crude productconduit 128. Other process streams and/or crudes enter blending zone 130directly or via stream conduit 132 and are combined with the crudeproduct to form a blended product. The blended product exits blendingzone 130 via blend conduit 134.

In some embodiments, the crude product and/or the blended product aretransported to a refinery and distilled and/or fractionally distilled toproduce one or more distillate fractions. The distillate fractions maybe processed to produce commercial products such as transportation fuel,lubricants, or chemicals.

In some embodiments, after contact of the crude feed with the catalyst,the crude product has a TAN of at most 90%, at most 50%, at most 30%, orat most 10% of the TAN of the crude feed. In certain embodiments, thecrude product has a TAN of at most 1, at most 0.5, at most 0.3, at most0.2, at most 0.1, or at most 0.05. TAN of the crude product willfrequently be at least 0.0001 and, more frequently, at least 0.001. Insome embodiments, TAN of the crude product may be in a range from about0.001 to about 0.5, about 0.01 to about 0.2, or about 0.05 to about 0.1.

In some embodiments, the crude product has a total Ni/V/Fe content of atmost 90%, at most 50%, at most 30%, at most 10%, at most 5%, or at most3% of the Ni/V/Fe content of the crude feed. In certain embodiments, thecrude product has, per gram of crude product a total Ni/V/Fe content ina range from about 1×10⁻⁷ grams to about 5×10⁻⁵ grams, about 3×10⁻⁷grams to about 2×10⁻⁵ grams, or about 1×10⁻⁶ grams to about 1×10⁻⁵grams. In certain embodiments, the crude product has at most 2×10⁻⁵grams of Ni/V/Fe per gram of crude product. In some embodiments, a totalNi/V/Fe content of the crude product is about 70% to about 130%, about80% to about 120%, or about 90% to about 110% of the Ni/V/Fe content ofthe crude feed.

In some embodiments, the crude product has a total content of metals inmetal salts of organic acids of at most 90%, at most 50%, at most 30%,at most 10%, or at most 5% of the total content of metals in metal saltsof organic acids in the crude feed. In some embodiments, the totalcontent of metals in metal salts of organic acids is in a range fromabout 0.1% to about 75%, from about 0.5% to about 45%, from about 1% toabout 25%, or from about 2% to about 9% of the content of metals inmetal salts of organic acids of the crude feed. Organic acids thatgenerally form metal salts include, but are not limited to, carboxylicacids, thiols, imides, sulfonic acids, and sulfonates. Examples ofcarboxylic acids include, but are not limited to, naphthenic acids,phenanthrenic acids, and benzoic acid. The metal portion of the metalsalts may include alkali metals (for example, lithium, sodium, andpotassium), alkaline-earth metals (for example, magnesium, calcium, andbarium), Column 12 metals (for example, zinc and cadmium), Column 15metals (for example arsenic), Column 6 metals (for example, chromium),or mixtures thereof.

In some embodiments, the crude product has a total content of alkalimetal and alkaline-earth metal in metal salts of organic acids of atmost 90%, at most 80%, at most 50%, at most 30%, at most 10%, or at most5% of the content of alkali metal and alkaline-earth metal in metalsalts of organic acids in the crude feed. In some embodiments, the totalcontent of alkali metal and alkaline-earth metal in metal salts oforganic acids in the crude product is in a range from about 0.1% toabout 75%, from about 0.5% to about 45%, from about 1% to about 25%, orfrom about 2% to about 9% of the total content of alkali metal andalkaline-earth metal salts of organic acids in the crude feed.

In certain embodiments, the crude product has a total content of zincsalts of one or more organic acids of at most 90%, at most 80%, at most50%, at most 30%, at most 10%, or at most 5% of the content of zincsalts of one or more organic acids in the crude feed. In someembodiments, the total content of zinc salts of organic acids in thecrude product is in a range from about 0.1% to about 75%, from about0.5% to about 45%, from about 1% to about 25%, or from about 2% to about9% of the total content of zinc salts of organic acids in the crudefeed.

In some embodiments, the crude product has a total content of chromiumand/or arsenic in metal salts of organic acids of at most 90% of thecontent of chromium and/or arsenic in metal salts of organic acids inthe crude feed.

In certain embodiments, the crude product has, per gram of crudeproduct, from about 1×10⁻⁷ grams to about 5×10⁻⁵ grams, about 5×10⁻⁷grams to about 1×10⁻⁵ grams, or about 1×10⁻⁶ grams to about 5×10⁻⁶ gramsof alkali metal and alkaline-earth metal in metal salts of organicacids.

In certain embodiments, API gravity of the crude product produced fromcontact of the crude feed with catalyst, at the contacting conditions,is about 70% to about 130%, about 80% to about 120%, about 90% to about110%, or about 100% to about 130% of the API gravity of the crude feed.In certain embodiments, API gravity of the crude product is from about14 to about 40, about 15 to about 30, or about 16 to about 25.

In certain embodiments, the crude product has a viscosity of at most90%, at most 80%, at most 70%, at most 50%, at most 30%, at most 10%, orat most 5% of the viscosity of the crude feed. In some embodiments, theviscosity of the crude product is at most 90% of the viscosity of thecrude feed while the API gravity of the crude product is about 70% toabout 130%, about 80% to about 120%, or about 90% to about 110% of theAPI gravity the crude feed.

In some embodiments, the crude product has a total heteroatoms contentof at most 90%, at most 50%, at most 30%, at most 10%, or at most 5% ofthe total heteroatoms content of the crude feed. In certain embodiments,the crude product has a total heteroatoms content of at least 1%, atleast 30%, at least 80%, or at least 99% of the total heteroatomscontent of the crude feed.

In some embodiments, the sulfur content of the crude product may be atmost 90%, at most 50%, at most 30%, at most 10%, or at most 5% of thesulfur content of the crude feed. In certain embodiments, the crudeproduct has a sulfur content of at least 1%, at least 30%, at least 80%,or at least 99% of the sulfur content of the crude feed.

In some embodiments, total nitrogen content of the crude product may beat most 90%, at most 80%, at most 70%, at most 50%, at most 30% or atmost 10%, or at most 5% of a total nitrogen content of the crude feed.In certain embodiments, the crude product has a total nitrogen contentof at least 1%, at least 30%, at least 80%, or at least 99% of the totalnitrogen content of the crude feed. In certain embodiments, the crudeproduct has a total nitrogen content in a range from about 0.1% to about75%, from about 0.5% to about 45%, from about 1% to about 25%, or about2% to about 9% of the total nitrogen content of the crude feed. In someembodiments, the crude product has, per gram of crude product, a totalnitrogen content in a range from about 0.00001 grams to about 0.05grams, about 0.0001 grams to about 0.01 grams, or about 0.0005 grams toabout 0.001 grams.

In certain embodiments, basic nitrogen content of the crude product maybe at most 95%, at most 90%, at most 50%, at most 30%, at most 10%, orat most 5% of the basic nitrogen content of the crude feed. In certainembodiments, the crude product has a basic nitrogen content of at least1%, at least 30%, at least 80%, or at least 99% of the basic nitrogencontent of the crude feed.

In some embodiments, the oxygen content of the crude product may be atmost 90%, at most 50%, at most 30%, at most 10%, or at most 5% of theoxygen content of the crude feed. In certain embodiments, the oxygencontent of crude product may be least 1%, at least 30%, at least 80%, orat least 99% of the oxygen content of the crude feed. In someembodiments, the total content of carboxylic acid compounds of the crudeproduct may be at most 90%, at most 50%, at most 30%, at most 10%, or atmost 5% of the content of the carboxylic acid compounds in the crudefeed. In certain embodiments, the total content of carboxylic acidcompounds of the crude product may be at least 1%, at least 30%, atleast 80%, or at least 99% of the total content of carboxylic acidcompounds in the crude feed.

In some embodiments, selected organic oxygen compounds may be reduced inthe crude feed. In some embodiments, carboxylic acids and/or metal saltsof carboxylic acids may be chemically reduced before non-carboxyliccontaining organic oxygen compounds. Carboxylic acids and non-carboxyliccontaining organic oxygen compounds in a crude product may bedifferentiated through analysis of the crude product using generallyknown spectroscopic methods (for example, infrared analysis, massspectrometry, and/or gas chromatography).

The crude product, in certain embodiments, has an oxygen content of atmost 90%, at most 80%, at most 70%, or at most 50% of the oxygen contentof the crude feed, and TAN of the crude product is at most 90%, at most70%, at most 50%, at most 30% or at most 40% of the TAN of the crudefeed. In certain embodiments, the oxygen content of the crude productmay be at least 1%, at least 30%, at least 80%, or at least 99% of theoxygen content of the crude feed, and the crude product has a TAN of atleast 1%, at least 30%, at least 80%, or at least 99% of the TAN of thecrude feed.

Additionally, the crude product may have a content of carboxylic acidsand/or metal salts of carboxylic acids of at most 90%, at most 70%, atmost 50%, or at most 40% of the crude feed, and a content ofnon-carboxylic acid containing organic oxygen compounds within about 70%to about 130%, about 80% to about 120%, or about 90% to about 110% ofthe non-carboxylic acid containing organic oxygen compounds of the crudefeed.

In some embodiments, the crude product includes, in its molecularstructure, from about 0.05 grams to about 0.15 grams or from about 0.09grams to about 0.13 grams of hydrogen per gram of crude product. Thecrude product may include, in its molecular structure, from about 0.8grams to about 0.9 grams or from about 0.82 grams to about 0.88 grams ofcarbon per gram of crude product. A ratio of atomic hydrogen to atomiccarbon (H/C) of the crude product may be within about 70% to about 130%,about 80% to about 120%, or about 90% to about 110% of the atomic H/Cratio of the crude feed. A crude product atomic H/C ratio within about10% to about 30% of the crude feed atomic H/C ratio indicates thatuptake and/or consumption of hydrogen in the process is relativelysmall, and/or that hydrogen is produced in situ.

The crude product includes components with a range of boiling points. Insome embodiments, the crude product includes, per gram of the crudeproduct: at least 0.001 grams, or from about 0.001 grams to about 0.5grams of hydrocarbons with a boiling range distribution of at most 100°C. at 0.101 MPa; at least 0.001 grams, or from about 0.001 grams toabout 0.5 grams of hydrocarbons with a boiling range distributionbetween about 100° C. and about 200° C. at 0.101 MPa; at least 0.001grams, or from about 0.001 grams to about 0.5 grams of hydrocarbons witha boiling range distribution between about 200° C. and about 300° C. at0.101 MPa; at least 0.001 grams, or from about 0.001 grams to about 0.5grams of hydrocarbons with a boiling range distribution between about300° C. and about 400° C. at 0.101 MPa; and at least 0.001 grams, orfrom about 0.001 grams to about 0.5 grams of hydrocarbons with a boilingrange distribution between about 400° C. and about 538° C. at 0.101 MPa.

In some embodiments the crude product includes, per gram of crudeproduct, at least 0.001 grams of hydrocarbons with a boiling rangedistribution of at most 100° C. at 0.101 MPa and/or at least 0.001 gramsof hydrocarbons with a boiling range distribution between about 100° C.and about 200° C. at 0.101 MPa.

In some embodiments, the crude product may have at least 0.001 grams, orat least 0.01 grams of naphtha per gram of crude product. In otherembodiments, the crude product may have a naphtha content of at most 0.6grams, or at most 0.8 grams of naphtha per gram of crude product.

In some embodiments, the crude product has, per gram of crude product, adistillate content in a range from about 0.00001 grams to about 0.5grams, about 0.001 grams to about 0.3 grams, or about 0.002 grams toabout 0.2 grams.

In certain embodiments, the crude product has, per gram of crudeproduct, a VGO content in a range from about 0.00001 grams to about 0.8grams, about 0.001 grams to about 0.5 grams, about 0.005 grams to about0.4 grams, or about 0.01 grams to about 0.3 grams.

In some embodiments, the crude product has a residue content of at most90%, at most 70%, at most 50%, at most 30%, or at most 10% of theresidue content of the crude feed. In certain embodiments, the crudeproduct has a residue content of about 70% to about 130%, about 80% toabout 120%, or about 90% to about 110% of the residue content of thecrude feed. The crude product may have, per gram of crude product, aresidue content in a range from about 0.00001 grams to about 0.8 grams,about 0.0001 grams to about 0.5 grams, about 0.0005 grams to about 0.4grams, about 0.001 grams to about 0.3 grams, about 0.005 grams to about0.2 grams, or about 0.01 grams to about 0.1 grams.

In some embodiments, the C₅ asphaltenes content is at most 90%, at most80%, at most 70%, at most 50%, at most 30%, or at most 10% of the C₅asphaltenes content of the crude feed. In certain embodiments, the C₅asphaltenes content of the crude product is at least 10%, at least 60%,or at least 70% of the C₅ asphaltenes content of the crude feed. Thecrude product may have a C₅ asphaltenes content in a range from about0.1% to about 75%, from about 0.5% to about 45%, from about 1% to about25%, or from about 2% to about 9% of the C₅ asphaltenes content of thecrude feed. The crude product has, in some embodiments, from about0.0001 grams to about 0.1 grams, from about 0.005 grams to about 0.08grams, or from about 0.01 grams to about 0.05 grams of C₅ asphaltenesper gram of crude product.

In certain embodiments, the crude product has an MCR content that is atmost 90%, at most 80%, at most 50%, at most 30%, or at most 10% of theMCR content of the crude feed. In some embodiments, the crude producthas a MCR content in a range from about 0.1% to about 75%, from about0.5% to about 45%, from about 1% to about 25%, or from about 2% to about9% of the MCR content of the crude feed. The crude product has, in someembodiments, from about 0.00001 grams to about 0.1 grams, about 0.0001grams to about 0.05 grams, or about 0.001 grams to about 0.005 grams ofMCR per gram of crude product.

In some embodiments, the C₅ asphaltenes content and MCR content may becombined to produce a mathematical relationship between the highviscosity components in the crude product relative to the high viscositycomponents in the crude feed. For example, a sum of a crude feed C₅asphaltenes content and a crude feed MCR content may be represented byS. A sum of a crude product C₅ asphaltenes content and a crude productMCR content may be represented by S′. The sums may be compared (S′ to S)to assess the net reduction in high viscosity components in the crudefeed. S′ of the crude product may be in a range from about 1% to about99%, about 10% to about 90%, or about 20% to about 80% of S. In someembodiments, a ratio of MCR content of the crude product to C₅asphaltenes content is in a range from about 1.0 to about 3.0, about 1.2to about 2.0, or about 1.3 to about 1.9.

In some embodiments, the crude product includes from greater than 0grams, but less than 0.01 grams, from about 0.000001 grams to about0.001 grams, or from about 0.00001 grams to about 0.0001 grams of totalcatalyst per gram of crude product. The catalyst may assist instabilizing the crude product during transportation and/or treatment.The catalyst may inhibit corrosion, inhibit friction, and/or increasewater separation abilities of the crude product. Methods describedherein may be configured to add one or more catalysts described hereinto the crude product during treatment.

The crude product produced from contacting system 100 (as shown in FIGS.1-6) has properties different than properties of the crude feed. Suchproperties may include, but are not limited to: a) reduced TAN; b)reduced viscosity; c) reduced total Ni/V/Fe content; d) reduced contentof sulfur, oxygen, nitrogen, or combinations thereof; e) reduced residuecontent; f) reduced C₅ asphaltenes content; g) reduced MCR content; h)increased API gravity; i) a reduced content of metals in metal salts oforganic acids; j) increased stability relative to the crude feed; or k)combinations thereof.

Catalysts used in one or more embodiments of the inventions may includeone or more bulk metals and/or one or more metals on a support. Themetals may be in elemental form or in the form of a compound of themetal. The catalysts described herein may be introduced into thecontacting zone as a precursor, and then become active as a catalyst inthe contacting zone (for example, when sulfur and/or a crude feedcontaining sulfur is contacted with the precursor). The catalyst orcombination of catalysts used as described herein may or may not becommercial catalysts. Examples of commercial catalysts that arecontemplated to be used as described herein include HDS22; HDN60; C234;C311; C344; C411; C424; C344; C444; C447; C454; C448; C524; C534; DN120;DN140; DN190; DN200; DN800; DC2118; DC2318; DN3100; DN3110; DN3300;DN3310; RC400; RC410; RN412; RN400; RN410; RN420; RN440; RN450; RN650;RN5210; RN5610; RN5650; RM430; RM5030; Z603; Z623; Z673; Z703; Z713;Z723; Z753; and Z763, which are available from CRI International, Inc.(Houston, Tex., U.S.A.).

In some embodiments, catalysts used to change properties of the crudefeed include one or more Columns 5-10 metal(s) on a support. Columns5-10 metal(s) include, but are not limited to, vanadium, chromium,molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt,nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum, ormixtures thereof. Compounds of Columns 5-10 metal(s) include, but arenot limited to, oxides, nitrates, ammonium salts, and carbonates of theColumns 5-10 metal(s). Examples of Columns 5-10 metal compounds include,but are not limited to, molybdenum trioxide, molybdenum ammonium oxide,molybdenum carbonate, tungsten trioxide, nickel oxide, nickel carbonate,nickel nitrate, cobalt carbonate, and cobalt oxide.

The catalyst may have, per gram of catalyst, a total Columns 5-10metal(s) content in a range from at least 0.0001 grams, at least 0.001grams, at least 0.01 grams, at least 0.3 grams, at least 0.5 grams, atleast 0.6 grams, at least 0.8 grams, or at least 0.9 grams. A totalcontent of Columns 5-10 metal(s), per gram of catalyst, may be in arange about 0.0001 grams to about 0.99 grams, about 0.0005 grams toabout 0.5 grams, about 0.001 grams to about 0.3 grams, about 0.005 gramsto about 0.2 grams, or about 0.01 grams to about 0.1 grams. In someembodiments, the catalyst includes Column 15 element(s) in addition tothe Columns 5-10 metal(s). An example of a Column 15 element isphosphorus. The catalyst may have a total Column 15 element content, pergram of catalyst, in range from about 0.000001 grams to about 0.1 grams,about 0.00001 grams to about 0.06 grams, about 0.00005 grams to about0.03 grams, or about 0.0001 grams to about 0.001 grams. In otherembodiments, the catalyst does not include a Column 15 element.

In some embodiments, the catalyst includes a combination of Column 6metal(s) with one or more metals from Column 5 and/or Columns 7-10. Amolar ratio of Column 6 metal to Column 5 metal may be in a range fromabout 0.1 to about 20, about 1 to about 10, or about 2 to about 5. Amolar ratio of Column 6 metal to Columns 7-10 metal may be in a rangefrom about 0.1 to about 20, about 1 to about 10, or about 2 to about 5.In some embodiments, the catalyst includes Column 15 element(s) inaddition to the combination of Column 6 metal(s) with one or more metalsfrom Columns 5 and/or 7-10. In other embodiments, the catalyst includesColumn 6 metal(s) and Column 10 metal(s). A molar ratio of the totalColumn 10 metal to the total Column 6 metal in the catalyst may be in arange from about 1 to about 10, or from about 2 to about 5. In certainembodiments, the catalyst includes Column 5 metal(s) and Column 10metal(s). A molar ratio of the total Column 10 metal to the total Column5 metal in the catalyst may be in a range from about 1 to about 10, orfrom about 2 to about 5.

In certain embodiments, the catalyst includes Column 6 metal(s). Thecatalyst may have, per gram of catalyst, a total Column 6 metal(s)content of at least 0.00001 grams, at least 0.01 grams, at least 0.02grams and/or in a range from about 0.0001 grams to about 0.6 grams,about 0.001 grams to about 0.3 grams, about 0.005 grams to about 0.2grams, or about 0.01 grams to about 0.1 grams. In some embodiments, thecatalyst includes from about 0.0001 grams to about 0.2 grams, from about0.001 grams to about 0.08 grams, or from about 0.01 grams to 0.06 gramsof Column 6 metal(s) per gram of catalyst. In some embodiments, thecatalyst includes Column 15 element(s) in addition to the Column 6metal(s).

In some embodiments, the catalyst includes a combination of Column 6metal(s) with one or more metals from Columns 7-10. The catalyst mayhave, per gram of catalyst, a total Column 7-10 metal(s) content in arange from about 0.0001 grams to about 0.1 grams, from about 0.001 gramsto about 0.05 grams, or from about 0.01 grams to about 0.03 grams. Incertain embodiments, the catalyst includes, per gram of catalyst, fromabout 0.01 grams to about 0.15 grams of molybdenum and from about 0.001grams to about 0.05 grams of nickel. The catalyst, in some embodiments,also includes from about 0.001 grams to about 0.05 grams of iron pergram of catalyst.

In some embodiments, the catalyst includes, per gram of catalyst, fromabout 0.01 grams to about 0.15 grams of molybdenum, from about 0.001grams to about 0.05 grams of nickel, from about 0.001 grams to about0.05 grams of iron, and from about 0.0001 grams to about 0.05 grams ofphosphorus.

In some embodiments, Columns 5-10 metal(s) are incorporated in, ordeposited on, a support to form the catalyst. In certain embodiments,Columns 5-10 metal(s) in combination with Column 15 element(s) areincorporated in, or deposited on, the support to form the catalyst. Inembodiments in which the metal(s) and/or element(s) are supported, theweight of the catalyst includes all support, all metal(s), and allelement(s). The support may be porous and may include refractory oxides,porous carbon based materials, zeolites, or combinations thereof.Refractory oxides may include, but are not limited to, alumina, silica,silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, ormixtures thereof. Supports may be obtained from a commercialmanufacturer such as Criterion Catalysts and Technologies LP (Houston,Tex., U.S.A.). Porous carbon based materials include, but are notlimited to, activated carbon and/or porous graphite. Examples ofzeolites include Y-zeolites, beta zeolites, mordenite zeolites, ZSM-5zeolites, and ferrierite zeolites. Zeolites may be obtained from acommercial manufacturer such as Zeolyst (Valley Forge, Pa., U.S.A.). Thesupport may be prepared and/or selected based upon a variety of desiredcharacteristics. Examples of characteristics include, but are notlimited to, pore volume, average pore diameter, pore volumedistribution, surface area, and percentage of pores above or in acertain pore diameter range.

The support, in some embodiments, is prepared such that the support hasan average pore diameter of at least 90 Å, at least 110 Å, at least 130Å, at least 150 Å, at least 170 Å, or at least 180 Å. In certainembodiments, the support is prepared by combining water with the supportto form a paste. In some embodiments, an acid is added to the paste toassist in extrusion of the paste. The water and dilute acid are added insuch amounts and by such methods as required to give the extrudablepaste a desired consistency. Examples of acids include, but are notlimited to, nitric acid, acetic acid, sulfuric acid, and hydrochloricacid.

The paste may be extruded and cut using generally known catalystextrusion methods and catalyst cutting methods to form extrudates. Theextrudates may be heat-treated at a temperature in a range from about65° C. to about 260° C. or from about 85° C. to about 235° C. for aperiod of time (for example, for about 0.5 hours to about 8 hours)and/or until the moisture content of the extrudate has reached a desiredlevel. The heat-treated extrudate may be further heat-treated at atemperature in a range from about 800° C. to about 1200° C. or about900° C. to about 1100° C. to form a support having an average porediameter of at least 150 Å. The supports have a pore volume distributionover a range of pore diameters. In some embodiments, the supportcontains pores that have a pore diameter of at least 350 Å, at least 400Å, at least 500 Å, or at least 1000 Å, or in a range of about 350 Å toabout 5000 Å, about 400 Å to about 1000 Å, or about 500 Å to about 900Å, which provide at most 15%, at most 10%, at most 5% at most 3%, atmost 1% or at most 0.5% of the total pore volume of the support.

In certain embodiments, the support includes gamma alumina, thetaalumina, delta alumina, alpha alumina, or combinations thereof. Theamount of gamma alumina, delta alumina, alpha alumina, or combinationsthereof, per gram of catalyst support, may be in a range from about0.0001 grams to about 0.99 grams, about 0.001 grams to about 0.5 grams,about 0.01 grams to about 0.1 grams, or at most 0.1 grams as determinedby x-ray diffraction. In some embodiments, the support includes, pergram of support, at least 0.5 grams, at least 0.8 grams, at least 0.9grams, or at least 0.95 grams of gamma alumina. In certain embodiments,the support contains, per gram of support, from about 0.5 grams to about0.99 grams, from about 0.6 grams to about 0.9 grams, or from about 0.7grams to about 0.8 grams of gamma alumina. In certain embodiments, thesupport has, either alone or in combination with other forms of alumina,a theta alumina content, per gram of support, in a range from about 0.1grams to about 0.99 grams, about 0.5 grams to about 0.9 grams, or about0.6 grams to about 0.8 grams, as determined by x-ray diffraction. Insome embodiments, the support may have, per gram of support, at least0.1 grams, at least 0.3 grams, at least 0.5 grams, or at least 0.8 gramsof theta alumina, as determined by x-ray diffraction.

In certain embodiments, the support includes, per gram of support, atmost 0.2 grams, at most 0.1 grams, at most 0.08 grams, at most 0.06grams, at most 0.05 grams, at most 0.04 grams, at most 0.03 grams, atmost 0.02 grams, or at most 0.01 grams of silica. In certainembodiments, the support has, per gram of support, from about 0.001grams to about 0.2 grams or from about 0.01 grams to about 0.1 grams ofsilica. In some embodiments, the support includes a combination ofsilica and alumina.

Supported catalysts may be prepared using generally known catalystpreparation techniques. Examples of catalyst preparations are describedin U.S. Pat. No. 6,218,333 to Gabrielov et al.; U.S. Pat. No. 6,290,841to Gabrielov et al.; and U.S. Pat. No. 5,744,025 to Boon et al., andU.S. Patent Application Publication No. US 2003/0111391 to Bhan, all ofwhich are incorporated herein by reference.

In some embodiments, the support may be combined with metal to form acatalyst. In certain embodiments, the support is heat-treated attemperatures in a range from about 400° C. to about 1200° C., about 450°C. to about 1000° C., or about 600° C. to about 900° C. prior tocombining with a metal. In some embodiments, impregnation aids may beused during preparation of the catalyst. Examples of impregnation aidsinclude hydrogen peroxide, organic acids, amines,ethylenediaminetetraacetic acid (EDTA), ammonia, or mixtures thereof.Examples of amines include, but are not limited to, alkanolamines,ammonia, alkyl amines, aromatic amines, and substituted ammoniumcompounds. Organic acids include, but are not limited to, citric acid,tartaric acid, oxalic acid, malonic acid, malic acid, or mixturesthereof.

In certain embodiments, the support may be combined with a metalsolution having a pH of up to about 3. The pH of the metal solution mayrange from about 1 to about 3, or from about 1.5 to about 2.5.Controlling the pH of the metal solution may facilitate dispersion ofmetals into the support. A dispersed or substantially dispersed metalcatalyst prepared using such pH controlled conditions may have anincreased catalyst life compared to the life of a conventional catalystwhen used to process a crude feed at the same contacting conditions.

The metal solution may include Column 6 metal(s). In some embodiments,the metal solution includes Column 6 metal(s) in combination withColumns 7-10 metal(s). In certain embodiments, the metal solutionincludes Column 15 element(s) in combination with Column 6 metal(s), orin combination with Column 6 metal(s) and Columns 7-10 metal(s).

In some embodiments, the pH of the metal solution may be adjusted to thedesired pH of up to pH 3 using mineral acids and/or organic acidcomponents. Mineral acids include, but are not limited to, phosphoricacid, nitric acid, sulfuric acid, or mixtures thereof.

In certain embodiments, the metal solution is prepared by combining oneor more Columns 6-10 metal solutions having different pH values. AColumns 6-10 metal solution having a pH in a range from about 4 to about7, or from about 5 to about 6, may be combined with a different Columns6-10 metal solution having a pH in a range from about 0.1 to about 4, orabout 1 to about 3. In some embodiments, the Columns 6-10 metalsolutions include impregnation aids, mineral acids, organic acids,Column 15 element(s), or mixtures thereof.

In certain embodiments, a catalyst may be formed by adding orincorporating multiple Columns 5-10 metal(s) to a support sequentially(“overlaying”). Overlaying a metal on top of a support that includes asubstantially uniform concentration of metal often provides beneficialcatalytic properties of the catalyst. Heat-treating the support aftereach overlay of metal tends to improve the catalytic activity of thecatalyst. Methods to prepare a catalyst using overlay methods aredescribed in U.S. Patent Application Publication No. US 2003/0111391 toBhan.

In some embodiments, a support/Columns 7-10 metal(s) mixture is preparedby combining a support with one or more Columns 7-10 metal(s). In anembodiment, the resulting mixture includes about 0.01 grams to about 0.1grams of Columns 7-10 metal(s) per gram of the support/Columns 7-10metal(s) mixture. The support/Columns 7-10 metal(s) mixture may beheat-treated at a temperature in a range from about 50° C. to about 100°C. or about 60° C. to about 90° C. for several hours, and thenheat-treated at a temperature in a range from about 400° C. to about700° C., about 450° C. to about 650° C., or about 500° C. to about 600°C. for about 2 hours. The resulting metal-containing support may becombined with a Column 6 metal(s) and, optionally, an additional amountof Columns 7-10 metal(s) such that the finished catalyst contains, pergram of catalyst, at least 0.3 grams, at least 0.1 grams, or at least0.08 grams of the Column 6 metal(s), and a total Columns 7-10 metal(s),per gram of catalyst, in a range from about 0.01 grams to about 0.2grams or from about 0.05 grams to about 0.1 grams. The resultingcatalyst may be heat-treated at a temperature in a range from about 50°C. to about 100° C. or from about 60° C. to about 90° C. for severalhours, and then heat-treated at a temperature in a range from about 350°C. to about 500° C. or 400° C. to about 450° C. for about 2 hours. Insome embodiments, Column 15 element(s) may be combined with thesupport/Columns 7-10 metal(s) mixture and/or with the Column 6 metal(s).

Typically, the Columns 5-10 metal(s) and support may be mixed withsuitable mixing equipment to form a Columns 5-10 metal(s)/supportmixture. Examples of suitable mixing equipment include tumblers,stationary shells or troughs, Muller mixers (for example, batch type orcontinuous type), impact mixers, and any other generally known mixer ordevice, that will suitably provide the Columns 5-10 metal(s)/supportmixture. In certain embodiments, the materials are mixed until theColumns 5-10 metal(s) is (are) substantially homogeneously dispersed inthe support.

In some embodiments, the catalyst is heat-treated at temperatures fromabout 150° C. to about 750° C., from about 200° C. to about 740° C., orfrom about 400° C. to about 730° C. after combining the support with themetal.

In some embodiments, the catalyst may be heat-treated in the presence ofhot air and/or oxygen rich air at a temperature in a range between about400° C. and about 1000° C. to remove volatile matter such that at leasta portion of the Columns 5-10 metal(s) are converted to thecorresponding metal oxide(s).

In other embodiments, however, the catalyst may be heat-treated in thepresence of air at temperatures in a range from about 35° C. to about500° C. for a period of time in a range from 1 hour to about 3 hours toremove a majority of the volatile components without substantiallyconverting the Columns 5-10 metal(s) to metal oxide(s). Catalystsprepared by such a method are generally referred to as “uncalcined”catalysts. When catalysts are prepared in this manner, in combinationwith a sulfiding method, the active metals may be substantiallydispersed on the support. Preparations of such catalysts are describedin U.S. Pat. No. 6,218,333 to Gabrielov et al. and U.S. Pat. No.6,290,841 to Gabrielov et al.

In certain embodiments, a theta alumina support may be combined withColumns 5-10 metal(s) to form a theta alumina support/Columns 5-10metal(s) mixture. The theta alumina support/Columns 5-10 metal(s)mixture may be heat-treated at a temperature of at least 400° C. to forma catalyst having a pore size distribution with a median pore diameterof at least 230 Å. Typically, such heat-treating is conducted attemperatures of at most 1200° C.

In some embodiments, bulk metals catalysts used to change properties ofthe crude feed include one or more Columns 6-10 metal(s). The bulk metalcatalyst may have, per gram of catalyst, a total Columns 6-10 metal(s)content from at least 0.3 grams, at least 0.5 grams, at least 0.6 grams,at least 0.8 grams, or at least 0.9 grams. The total Columns 6-10metal(s) content, per gram of catalyst, may be in a range from about 0.3grams to about 0.99 grams, from about 0.5 grams to about 0.9 grams, orfrom about 0.6 grams to about 0.8 grams.

In some embodiments, the catalyst includes Column 15 element(s) inaddition to the Columns 6-10 metal(s). The bulk metal catalyst may havea total Column 15 element content, per gram of catalyst, in range fromabout 0.000001 grams to 0.1 grams, about 0.00001 grams about 0.06 grams,about 0.00005 grams to about 0.03 grams, or about 0.0001 grams to about0.001 grams.

The bulk metal catalyst, in some embodiments, may include a binder. Thebinder may be silica, alumina oxide, zinc oxide, oxides of the Columns6-10 metal(s), carbon, zeolites, or mixtures thereof. In certainembodiments, the catalyst includes at most 0.2 grams, at most 0.1 grams,at most 0.05 grams, at most 0.01 grams, or at most 0.005 grams of binderper gram of catalyst.

The bulk metal catalyst may be prepared as described in U.S. Pat. No.4,937,218 to Aqudelo et al.; U.S. Pat. No. 6,162,350 to Soled et al.;and U.S. Pat. No. 6,783,663 to Riley et al.; U.S. Patent ApplicationPublication Nos. US 2004/0182749 to Domokos et al. and US 2004/0235653to Domokos et al.; and by Landau et al. in “Hydrosulfurization ofMethyl-Substituted Dibenzothiophenes: Fundamental Study of Routes toDeep Desulfurization, Journal of Catalysis, 1996, Vol. 159, pp. 236-235,all of which are incorporated herein by reference.

In some embodiments, one or more Columns 6-10 metal slurries in water orother protic liquids are contacted at a temperature in a range fromabout 25° C. to about 95° C. with a slurry of water, alkaline compound,and a binder to form a Columns 6-10 metal/binder slurry. The Columns6-10 metal slurries may include 0.01 grams to 0.8 grams, 0.02 grams to0.5 grams, or 0.05 grams to 0.3 grams of Columns 6-10 metal(s) per gramof slurry. In some embodiments, the alkali compound is ammonia. Anamount of alkali compound may be at least 0.5 moles, at least 0.7 moles,at least 0.8 moles, at least, 0.9 moles or at most 2 mole per mole ofColumns 6-10 metal(s), based on the oxide form of the Columns 6-10metal(s). In some embodiments, the binder may be silica, alumina,silica/alumina, titanium oxide, zirconium oxide, or mixtures thereof.

The Columns 6-10 metal/binder slurry may be held at ambient and/or atthe slurry temperature for a period of time (for example, at least 10minutes, at least 30 minutes, or at least 240 minutes) and then cooled,if necessary. The bulk metal catalyst may be isolated from the slurryusing general isolation techniques (for example, filtration, spraydying, flash drying, evaporation, and vacuum distillation). The bulkmetal catalyst may be heat-treated in a range from about 25° C. to 95°C., from about 55° C. to about 90° C., or from about 70° C. to about 80°C. In some embodiments, the bulk metal catalyst is further heat-treatedat a temperature in a range from about 100° C. to about 600° C., fromabout 120° C. to about 400° C., or at most 300° C. In certainembodiments, the bulk metal catalyst may be powdered, shaped, and/orcombined with other materials.

The bulk metal catalyst may be characterized using powder x-raydiffraction methods. In some embodiments, the bulk metal catalyst mayexhibit no significant reflection that can be assigned to the Columns6-10 metal components. No significant reflection as detected by x-raydiffraction methods may indicate that the bulk metal catalyst issubstantially amorphous, or amorphous.

In some embodiments, the support (either a commercial support or asupport prepared as described herein) may be combined with a supportedcatalyst and/or a bulk metal catalyst. In some embodiments, thesupported catalyst may include Column 15 element(s). For example, thesupported catalyst and/or the bulk metal catalyst may be converted intoa powder with an average particle size from about 1 micron to about 50microns, about 2 microns about 45 microns, or about 5 microns to about40 microns. The powder may be combined with a support to form anembedded metal catalyst. In some embodiments, the powder may be combinedwith the support and then extruded using standard techniques to form acatalyst having a pore size distribution with a median pore diameter ina range from about 80 Å to about 200 Å or about 90 Å to about 180 Å, orabout 120 Å to about 130 Å. Combining the catalyst with the supportallows, in some embodiments, at least a portion of the metal to resideunder the surface of the resulting embedded metal catalyst leading toless metal on the surface than would otherwise occur in the unembeddedmetal catalyst. In some embodiments, having less metal on the surface ofthe catalyst extends the life and/or catalytic activity of the catalystby allowing at least a portion of the metal to move to the surface ofthe catalyst during use. The metals may move to the surface of thecatalyst through erosion of the surface of the catalyst during contactof the catalyst with a crude feed.

In some embodiments, catalysts may be characterized by pore structure.Various pore structure parameters include, but are not limited to, porediameter, pore volume, surface areas, or combinations thereof. Thecatalyst may have a distribution of total quantity of pore size versuspore diameter. The median pore diameter of the pore size distributionmay be in a range from about 30 Å to about 1000 Å, about 50 Å to about500 Å, or about 60 Å to about 300 Å. In some embodiments, catalysts thatinclude at least 0.5 grams of gamma alumina per gram of catalyst have apore size distribution with a median pore diameter in a range from about50 Å to about 500 Å, about 60 Å to about 200 Å, about 90 Å to about 180Å, about 100 Å to about 140 Å, or about 120 Å to about 130 Å. In otherembodiments, catalysts that include at least 0.1 grams of theta aluminaper gram of catalyst have a pore size distribution with a median porediameter in a range from about 180 Å to about 500 Å, about 200 Å toabout 300 Å, or about 230 Å to about 250 Å. Such median pore diametersare typically at most 1000 Å.

In certain embodiments, the median pore diameter of the pore sizedistribution is greater than 110 Å, at least 120 Å, at least 130 Å, atleast 140 Å, at least 150 Å, at least 200 Å, or at least 250 Å. Suchmedian pore diameters are typically at most 300 Å. The median porediameter of the pore size distribution may be in a range from about 115Å to about 290 Å, from about 120 Å to about 190 Å, from about 130 Å toabout 180 Å, or from about 140 Å to about 160 Å.

In some embodiments, the catalyst having the pore size distribution hasat least 60% of a total number of pores in the pore size distributionwith a pore diameter within about 45 Å, about 35 Å, about 30 Å, about 25Å, or about 20 Å of the median pore diameter of the pore distribution.In embodiments in which the median pore diameter of the pore sizedistribution is at least 180 Å, at least 200 Å, or at least 230 Å,greater that 60% of a total number of pores in the pore sizedistribution have a pore diameter within about 50 Å, about 70 Å, orabout 90 Å of the median pore diameter. In some embodiments, thecatalyst has a pore size distribution with a median pore diameter in arange from about 180 Å to about 500 Å, about 200 Å to about 400 Å, orabout 230 Å to about 300 Å, with at least 60% of a total number of poresin the pore size distribution having a pore diameter within about 50 Å,about 70 Å, or about 90 Å of the median pore diameter.

In some embodiments, pore volume of pores may be at least 0.3 cm³/g, atleast 0.7 cm³/g or at least 0.9 cm³/g. In certain embodiments, porevolume of pores may range from about 0.3 cm³/g to about 0.99 cm³/g,about 0.4 cm³/g to about 0.8 cm³/g, or about 0.5 cm³/g to about 0.7cm³/g. In some embodiments, pores having a pore diameter of at least 350Å, at least 400 Å, at least 500 Å, at least 1000 Å, at least 3000 Å, orat least 5000 Å provide at most 10%, at most 5%, at most 3%, at most 1%,or at most 0.5% of the total pore volume of the catalyst. Such porediameters may be in a range of about 350 Å to about 5000 Å, about 400 Åto about 1000 Å, or about 500 Å to about 900 Å. The total pore volumeprovided by pores with such pore diameters may be in a range from about0% to about 9%, about 0.1% to about 5%, or about 0.5% to about 1%.

The catalyst having a pore size distribution with a median pore diameterin a range from about 60 Å to about 500 Å may, in some embodiments, havea surface area of at least 100 m²/g, at least 120 m²/g, at least 170m²/g, at least 220 m²/g, or at least 270 m²/g. Such surface area may bein a range from about 100 m 2/g to about 300 m²/g, about 120 m²/g toabout 270 m²/g, about 130 m²/g to about 250 m²/g, or about 170 m²/g toabout 220 m²/g. In certain embodiments, a surface area of a shaped bulkmetal catalyst is at least 30 m²/g, at least 60 m²/g, or in a range fromabout 10 m²/g to about 350 m²/g.

In some embodiments, the bulk metal catalyst, the supported catalystand/or the catalyst precursor is sulfided to form metal sulfides (priorto use) using techniques known in the art (for example, ACTICAT™process, CRI International, Inc.). In some embodiments, the catalyst(s)and/or catalyst precursor may be dried then sulfided. Alternatively, thecatalyst(s) or catalyst precursor may be sulfided in situ by contact ofthe catalyst or catalyst precursor with a crude feed that includessulfur-containing compounds. In-situ sulfurization may utilize eithergaseous hydrogen sulfide in the presence of hydrogen, or liquid-phasesulfurizing agents such as organosulfur compounds (includingalkylsulfides, polysulfides, thiols, and sulfoxides). Ex-situsulfurization processes are described in U.S. Pat. No. 5,468,372 toSeamans et al. and U.S. Pat. No. 5,688,736 to Seamans et al., both ofwhich are incorporated herein by reference.

In certain embodiments, a first type of catalyst (“first catalyst”)includes Columns 5-10 metal(s) in combination with a theta aluminasupport. The first catalyst has a pore size distribution with a medianpore diameter of at least 180 Å, at least 220 Å, at least 230 Å, atleast 250 Å, at least 300 Å, or at most 500 Å. The support may includeat least 0.1 grams, at least 0.5 grams, or at least 0.9 grams, or atmost 0.999 grams of theta alumina per gram of support. In someembodiments, the support has an alpha alumina content of below 0.1 gramsof alpha alumina per gram of catalyst. The catalyst includes, in someembodiments, at most 0.1 grams of Column 6 metal(s) per gram of catalystand at least 0.0001 grams of Column 6 metal(s) per gram of catalyst. Insome embodiments, the Column 6 metal(s) are molybdenum and/or tungsten.In some embodiments, a first catalyst may include Column 5 metal(s). Thefirst catalyst may allow for removal of alkali metals and alkaline-earthmetals in metal salts of organic acids. The first catalyst is generallycapable of removing at least a portion of the alkali metals and/oralkaline-earth metal salts of organic acids, which may reduce viscosityand/or surface tension of the crude feed. This may allow the resultingcrude feed to be more readily contacted with catalysts positioned afterthe first catalyst.

In certain embodiments, a second type of catalyst (“second catalyst”)includes Columns 6-10 metal(s) in combination with a support. The secondcatalyst has a median pore diameter of greater than 110 Å. The secondcatalyst has pores with a pore diameter of at least 350 Å, which provideat most 10% of the pore volume of the second catalyst. The secondcatalyst has per gram of second catalyst, in some embodiments, a totalcontent of Column 6 metal(s) in a range from about 0.0001 grams to about0.3 grams, a total content of Columns 7-10 metal(s) in a range fromabout 0.0001 grams to about 0.1 grams, and a total content of Column 15element(s) in a range from about 0.00001 grams to about 0.1 grams. Incertain embodiments, the second catalyst support has, per gram ofsupport, at least 0.9 grams of gamma alumina. The second catalyst isgenerally capable of: removing at least a portion of the components fromthe crude feed that contribute to thermal degradation as measured byMCR; removing at least a portion of organic nitrogen containingcompounds; and removing at least a portion of the C₅ asphaltenes fromthe crude feed. The second catalyst, in some embodiments, also removesat least a portion of the residue, removes at least a portion of theNi/FeN, removes at least a portion of the components that contribute tohigh viscosities, and/or removes at least a portion of the componentsthat contribute to low API gravity.

In some embodiments, a third type of catalyst (“third catalyst”) mayhave a median pore diameter of about 250 Å. The third catalyst has poreswith a pore diameter of at least 350 Å, which provide at most 10% of thepore volume of the third catalyst. The third catalyst is generallycapable of: removing at least a portion of the components from the crudefeed that contribute to thermal degradation as measured by MCR; removinga portion of compounds containing heteroatoms; and/or removing a portionof the C₅ asphaltenes from the crude feed. The third catalyst, in someembodiments, also removes components that contribute to high viscositiesand/or low API gravity.

In some embodiments, the second catalyst(s) and third catalyst(s) haveselected median pore diameters and pores having selected pore diametersproviding at most 10%, at most 5%, at most 3% or at most 1% of the porevolume. These catalysts provide enhanced reduction of C₅ asphaltenescontent in the crude feed and/or reduction of at least a portion of thecomponents that contribute to thermal degradation of the crude feed asmeasured by MCR. Reduction of these compounds using catalysts withselected median pore diameter and selected pore volume may allow thenumber of catalysts to be minimized. Typically, the crude feed is firsttreated with a conventional catalyst having relatively low catalyticactivity to remove C₅ asphaltenes and/or components that contribute tothermal degradation. These types of conventional catalysts generallyremove the C₅ asphaltenes and/or other components by allowing arelatively large portion of the C₅ asphaltenes and/or other componentsto enter the pores of the catalysts and fill the pores. As the pores arefilled, the C₅ asphaltenes and/or other components may be physicallyremoved from the crude feed. Once the pores are filled and/or plugged,the life of the conventional catalyst becomes diminished. Catalysts withselected median pore diameter and selected pore volumes remove C₅asphaltenes and/or other components that contribute to thermaldegradation by limiting the portion, if any, of C₅ asphaltenes and/orother components that enter the pores of the catalyst. As such, the lifeof the catalyst may not be diminished due to contact of the catalystwith C₅ asphaltenes and/or other components.

In some embodiments, the second catalyst(s) and/or the third catalyst(s)may remove at least a portion of the alkali metals and alkaline-metalsin metal salts of organic acids. In certain embodiments, the secondcatalyst(s) and/or the third catalyst(s) are capable of removing atleast a portion of the alkali metals and/or alkaline-earth metal saltsof organic acids that contribute to formation of compounds that increaseviscosity and/or surface tension of the crude feed. In some embodiments,the second catalyst(s) and/or the third catalyst(s) are capable ofremoving at least a portion of the components that contribute torelatively high viscosity of the crude feed.

In some embodiments, a fourth type of catalyst (“fourth catalyst”) maybe obtainable by combining a support with Column 6 metal(s) to produce acatalyst precursor. Typically, the catalyst precursor is heated to atleast 100° C. for about 2 hours. In certain embodiments, the fourthcatalyst(s) may have, per gram of fourth catalyst(s), a Column 15element(s) content in a range from about 0.001 grams to about 0.03grams, 0.005 grams to about 0.02 grams, or 0.008 grams to about 0.01grams. The fourth catalyst(s) may exhibit significant activity andstability when used to treat the crude feed as described herein. In someembodiments, the catalyst precursor is heated at temperatures below 500°C. in the presence of one or more sulfur compounds. The fourthcatalyst(s) is (are) generally capable of removing a portion of nitrogencontaining compounds from the crude feed. Removal of nitrogen containingcompounds decreases the corrosive properties of the crude productrelative to the corrosive properties of the crude feed. The fourthcatalyst(s) may remove at least a portion of the components thatcontribute to the TAN of the crude feed, remove at least a portion ofthe metals in metal salts of organic acids, remove at least a portion ofthe NiN/Fe, and/or remove at least a portion of components contributingto a high viscosity of the crude feed.

The fourth catalyst(s), in some embodiments, may also reduce at least aportion of the MCR content of the crude feed, while maintaining crudefeed/total product stability. In certain embodiments, the fourthcatalyst(s) may have a Column 6 metal(s) content in a range from about0.0001 grams to about 0.1 grams, about 0.005 grams to about 0.05 grams,or about 0.001 grams to about 0.01 grams and a Column 10 metal(s)content in a range from about 0.0001 grams to about 0.05 grams, about0.005 grams to about 0.03 grams, or about 0.001 grams to about 0.01grams per gram of fourth catalyst(s). The fourth catalyst(s) mayfacilitate reduction of at least a portion of the components thatcontribute to MCR in the crude feed at temperatures in a range fromabout 300° C. to about 500° C. or about 350° C. to about 450° C. andpressures in a range from about 0.1 MPa to about 20 MPa, about 1 MPa toabout 10 MPa, or about 2 MPa to about 8 MPa.

In certain embodiments, a fifth type of catalyst (“fifth catalyst”) maybe a bulk metal catalyst. The fifth catalyst(s) includes at least 0.3grams of Columns 6-10 metal(s) per gram of fifth catalyst(s). In certainembodiments, the fifth catalyst(s) also includes the binder. The fifthcatalyst(s), in some embodiments, includes Column 6 metal(s) incombination with Column 9 metal(s) and/or Column 10 metal(s). The fifthcatalyst(s) is generally capable of removing at least a portion of thecomponents that contribute to thermal degradation as measured by MCR.The fifth catalyst(s), in some embodiments, is also capable of removingat least a portion of C₅ asphaltenes, at least a portion of organiccompounds containing heteroatoms, at least a portion of the totalNi/V/Fe content, at least a portion of the components that contribute tohigh viscosity, and/or at least a portion of the components thatcontribute to low API gravity.

The first catalyst(s), second catalyst(s), third catalyst(s), fourthcatalyst(s), and fifth catalyst(s), may be stable for at least 3 months,at least 6 months or at least 1 year at temperatures of at least 370°C., at least 380° C., at least 390° C., at least 400° C., or at least420° C., and pressures of at least 8 Nm³/m³, at least 10 Nm³/m³, or atleast 14 Nm³/m³ during contact with the crude feed.

In some embodiments, the crude feed may be contacted with an additionalcatalyst subsequent to contact with the first catalyst. The additionalcatalyst may be one or more of the following: the second catalyst, thethird catalyst, the fourth catalyst, the fifth catalyst, the commercialcatalysts described herein, or combinations thereof.

Other embodiments of the first catalyst(s), second catalyst(s), thirdcatalyst(s), fourth catalyst(s), and fifth catalyst(s) may also be madeand/or used as is otherwise described herein.

Selecting the catalyst(s) of this application and controlling operatingconditions may allow a crude product to be produced that has a MCRcontent, a nitrogen content, a content of metals in metal salts oforganic acids, and/or selected properties changed relative to the crudefeed. The resulting crude product may have enhanced properties relativeto the crude feed and, thus, be more acceptable for transporting and/orrefining.

Arrangement of two or more catalysts in a selected sequence may controlthe sequence of property improvements for the crude feed. For example,metals in metal salts of organic acids in the crude feed can be reducedbefore at least a portion of the components contributing to MCR and/orheteroatoms in the crude feed are reduced.

Arrangement and/or selection of the catalysts may, in some embodiments,improve lives of the catalysts and/or the stability of the crudefeed/total product mixture. Improvement of a catalyst life and/orstability of the crude feed/total product mixture during processing mayallow a contacting system to operate for at least 3 months, at least 6months, or at least 1 year without replacement of the catalyst in thecontacting zone. A life of the catalyst may be determined by measuringthe temperature change of the contacting zone over a period of time (forexample, one month, two months, three months, six months, and/or oneyear), while other contacting conditions remain relatively constant suchthat certain product specifications are maintained. A requirement for anincrease in the temperature of about 15° C., about 13° C., or about 10°C. above the initial temperature required for processing, may indicatethat the effectiveness of the catalyst is diminished.

Combinations of selected catalysts may allow reduction in at least aportion of the MCR content, at least a portion of the Ni/V/Fe, at leasta portion of the C₅ asphaltenes, at least a portion of the metals inmetal salts of organic acids, at least a portion of the components thatcontribute to TAN, at least a portion of the residue, or combinationsthereof, from the crude feed before other properties of the crude feedare changed, while maintaining the stability of the crude feed/totalproduct mixture during processing (for example, maintaining a crude feedP-value of above 1.5). Alternatively, C₅ asphaltenes, TAN, and/or APIgravity may be incrementally reduced by contact of the crude feed withselected catalysts. The ability to incrementally and/or selectivelychange properties of the crude feed may allow the stability of the crudefeed/total product mixture to be maintained during processing.

The first catalyst allows, in some embodiments, for removal of at leasta portion of metals in metal salts of organic acids from the crude feed.For example, reducing at least a portion of the metals in metal salts oforganic acids in the crude feed/total product mixture relative to thecrude feed inhibits plugging of other catalysts positioned downstream,and thus, increases the length of time the contacting system may beoperated without replenishment of catalyst. Removal of at least aportion of the metals in metal salts of organic acids from the crudefeed may, in some embodiments, increase a life of one or more catalystspositioned after the first catalyst.

The second catalyst(s), the third catalyst(s), and/or the fourthcatalyst(s) may be positioned downstream of the first catalyst. Furthercontact of the crude feed/total product mixture with the secondcatalyst(s), third catalyst(s), and/or the fourth catalyst(s) may reduceMCR content, reduce the content of NiN/Fe, reduce sulfur content, reduceoxygen content, reduce viscosity, and/or further reduce the content ofmetals in metal salts of organic acids.

In some embodiments, the fifth catalyst(s) may be positioned downstreamof commercial catalysts. The commercial catalysts may be used to removeat least a portion of the Ni/V/Fe in a crude feed. Further contact ofthe crude feed/total product mixture with the fifth catalyst(s) mayreduce MCR content, reduce sulfur content, reduce nitrogen content,and/or reduce oxygen content.

In some embodiments, catalyst selection and/or order of catalysts incombination with controlled contacting conditions (for example,temperature and/or crude feed flow rate) may assist in reducing hydrogenuptake by the crude feed, maintaining crude feed/total product mixturestability during processing, and changing one or more properties of thecrude product relative to the respective properties of the crude feed.Stability of the crude feed/total product mixture may be affected byvarious phases separating from the crude feed/total product mixture.Phase separation may be caused by, for example, insolubility of thecrude feed and/or crude product in the crude feed/total product mixture,flocculation of asphaltenes from the crude feed/total product mixture,precipitation of components from the crude feed/total product mixture,or combinations thereof.

At certain times during the contacting period, the concentration ofcrude feed and/or total product in the crude feed/total product mixturemay change. As the concentration of the total product in the crudefeed/total product mixture changes due to formation of the crudeproduct, solubility of the components of the crude feed and/orcomponents of the total product in the crude feed/total product mixturetends to change. For example, the crude feed may contain components thatare soluble in the crude feed at the beginning of processing. Asproperties of the crude feed change (for example, TAN, MCR, C₅asphaltenes, P-value, or combinations thereof), the components may tendto become less soluble in the crude feed/total product mixture. In someinstances, the crude feed and the total product may form two phasesand/or become insoluble in one another. Solubility changes may alsoresult in the crude feed/total product mixture forming two or morephases. Formation of two phases, through flocculation of asphaltenes,change in concentration of crude feed and total product, and/orprecipitation of components, tends to reduce the life of one or more ofthe catalysts. Additionally, the efficiency of the process may bereduced. For example, repeated treatment of the crude feed/total productmixture may be necessary to produce a crude product with desiredproperties.

During processing, the P-value of the crude feed/total product mixturemay be monitored and the stability of the process, crude feed, and/orcrude feed/total product mixture may be assessed. Typically, a P-valuethat is at most 1.5 indicates that flocculation of asphaltenes from thecrude feed generally occurs. If the P-value is initially at least 1.5,and such P-value increases or is relatively stable during contacting,then this indicates that the crude feed is relatively stabile duringcontacting. Crude feed/total product mixture stability, as assessed byP-value, may be controlled by controlling contacting conditions, byselection of catalysts, by selective ordering of catalysts, orcombinations thereof. Such controlling of contacting conditions mayinclude controlling LHSV, temperature, pressure, hydrogen uptake, crudefeed flow, or combinations thereof.

Catalysts described herein may facilitate reduction of MCR content andviscosity at elevated temperatures and pressures while maintaining thestability of the crude feed/total product mixture and/or maintaining thelives of the catalysts.

In some embodiments, contacting conditions are controlled such thattemperatures in one or more contacting zones may be different. Operatingat different temperatures allows for selective change in crude feedproperties while maintaining the stability of the crude feed/totalproduct mixture. The crude feed enters a first contacting zone at thestart of a process. A first contacting temperature is the temperature inthe first contacting zone. Other contacting temperatures (for example,second temperature, third temperature, fourth temperature, et cetera)are the temperatures in contacting zones that are positioned after thefirst contacting zone. A first contacting temperature may be in a rangefrom about 100° C. to about 420° C. and a second contacting temperaturemay be in a range that is about 20° C. to about 100° C., about 30° C. toabout 90° C., or about 40° C. to about 60° C. different than the firstcontacting temperature. In some embodiments, the second contactingtemperature is greater than the first contacting temperature. Havingdifferent contacting temperatures may reduce TAN and/or C₅ asphaltenescontent in a crude product relative to the TAN and/or the C₅ asphaltenescontent of the crude feed to a greater extent than the amount of TANand/or C₅ asphaltene reduction, if any, when the first and secondcontacting temperatures are the same as or within 10° C. of each other.

EXAMPLES

Non-limiting examples of support preparations, catalyst preparations,and systems with selected arrangement of catalysts and controlledcontacting conditions are set forth below.

Example 1 Preparation of a Catalyst Support

An alumina/silica support was prepared by mulling 550 grams of analumina/silica mixture, 26 grams of calcined alumina fines, 585 grams ofwater, and 8 grams of 16M nitric acid for 35 minutes. The alumina/silicamixture was prepared by combining at least 0.98 grams of alumina/silicamixture (Criterion Catalysts and Technologies LP) per gram of supportwith up to 0.02 grams of silica (Criterion Catalysts and TechnologiesLP) per gram of alumina/silica mixture. The mulled mixture was extrudedthrough 1.94 mm and 3.28 mm diameter die plates, and then heat-treatedat a temperature in a range from 93° C. (200° F.) to 121° C. (250° F.)until a loss on ignition in a range of 27 wt % to 30 wt %, based oninitial extrudate weight, was obtained. Loss on ignition was performedby heating the extrudates to 540° C. for 15 minutes to 50 minutes, andthen determining the relative amount of weight lost by the extrudates.The extrudates were further heat-treated at 918° C. (1685° F.) for 1hour. The support had an average pore diameter of 125 Å, a surface areaof 281 m 2/g, a pore volume of 0.875 cm³/g, and pores with a diameter ofat least 350 Å, which provided 0.9% of the total pore volume of thesupport. Example 1 demonstrates preparation of a support that has anaverage pore diameter of at least 90 Å and pores having a pore diameterof at least 350 Å provide at most 15% of the pore volume of the support.

Example 2 Preparation of a Catalyst having a Median Pore Diameter of 115Å and a Selected Pore Volume Distribution

A catalyst was prepared as follows. An alumina/silica support preparedas described in Example 1 was impregnated with amolybdenum/nickel/phosphorus impregnation solution prepared as follows.A first solution was made by combining 62.34 grams of (NH₄)₂Mo₂O₇, 17.49grams of MoO₃, 12.22 grams of 30% H₂O₂, and 50.47 grams of deionizedwater to form a slurry. MEA (3.0 grams) was added to the slurry at arate sufficient to control the exotherm of dissolution. The slurry washeated to 64° C. (147° F.) until the solids dissolved, and then cooledto room temperature. The pH of the first solution was 5.34.

A second solution was made by combining 8.2 grams of Ni(NO₃)₂-6H₂O and5.47 grams of NiCO₃ with 30.46 grams of deionized water, and then adding29.69 grams of 85 wt % H₃PO₄. The pH of the second solution was 0.29.The first solution and second solution were combined, and sufficientdeionized water was added to bring the combined solution volume up to218.75 mL to yield the molybdenum/nickel/phosphorus impregnationsolution. The pH of the impregnation solution was 2.02.

The support (200.0 grams) was combined with the impregnation solutionand aged for several hours with occasional agitation. The resultingsupport/metal mixture was heat-treated at 125° C. for several hours, andthen heat-treated at 482° C. (900° F.) for 2 hours. The resultingcatalyst contained, per gram of catalyst, 0.13 grams of molybdenum, 0.03grams of nickel, and 0.03 grams of phosphorus with the balance beingsupport. The catalyst had a pore size distribution with a median porediameter of 115 Å with 66.7% of the total number of pores having a porediameter within 28 Å of the median pore diameter. The surface area ofthe catalyst was 179 m²/g. The pore volume of the catalyst was 0.5cm³/g. The pore volume distribution is summarized in Table 1. TABLE 1 %of pore volume Range, Å Catalyst  <70 3.07  70-100 16.21 100-130 69.36130-150 7.81 150-180 0.86 180-200 0.37 200-240 0.47 240-300 0.39 300-3500.23 350-450 0.27 450-600 0.23  600-1000 0.27 1000-3000 0.22 3000-50000.72 >5000 0

As shown in Table 1, the pores of the catalyst having a pore diameter ofat least of 350 Å provided 1.71% of the total pore volume of thecatalyst.

Example 2 demonstrates preparation of a Column 6 metal catalyst having apore size distribution with a median pore diameter of greater than 110Å, and a pore volume in which pores having a pore diameter of at least350 Å provide at most 10% of the total pore volume. This example alsodemonstrates preparation of a Column 6 metal catalyst from a supporthaving an average pore diameter of at least 90 Å, and a pore volume inwhich pores having a pore diameter of at least 350 Å provide at most 15%of the total pore volume.

Example 3 Contact of a Crude Feed with Two Catalysts

A tubular reactor with a centrally positioned thermowell was equippedwith thermocouples to measure temperatures throughout a catalyst bed.The catalyst bed was formed by filling the space between the thermowelland an inner wall of the reactor with catalysts and silicon carbide(20-grid, Stanford Materials; Aliso Viejo, Calif.). Such silicon carbideis believed to have low, if any, catalytic properties under the processconditions described herein. All catalysts were mixed with siliconcarbide in a volume ratio of 2 parts silicon carbide to 1 part catalystbefore placing the mixture into the contacting zone portions of thereactor.

The crude feed flow to the reactor was from the top of the reactor tothe bottom of the reactor. Silicon carbide was positioned at the bottomof the reactor to serve as a bottom support. A bottom catalyst/siliconcarbide mixture (81 cm³) was positioned on top of the silicon carbide toform a bottom contacting zone. The bottom catalyst was prepared asdescribed in Example 2.

A top catalyst/silicon carbide mixture (9 cm³) was positioned on top ofthe bottom contacting zone to form a top contacting zone. The topcatalyst was a molybdenum/vanadium catalyst on a theta alumina supportprepared as follows. A support was prepared by mulling 576 grams ofalumina (Criterion Catalysts and Technologies LP, Michigan City,Michigan, U.S.A.) with 585 grams of water and 8 grams of glacial nitricacid for 35 minutes. The resulting mulled mixture was extruded through a1.3 mm die plate, heat-treated between 90° C. and about 125° C., andfurther heat-treated at 918° C., which resulted in 650 grams of asupport with a median pore diameter of 182 Å. The heat-treated supportwas placed in a Lindberg furnace. The furnace temperature was raised toabout 1000° C. to about 1100° C. over 1.5 hours, and then held in thisrange for 2 hours to produce the support. The support was impregnatedwith a molybdenum/vanadium impregnation solution prepared as follows. Afirst solution was made by combining 2.14 grams of (NH₄)₂Mo₂O₇, 3.21grams of MoO₃, 0.56 grams of 30% H₂O₂, 0.14 grams of monoethanolamine,and 3.28 grams of deionized water to form a slurry. The slurry washeated to 65° C. until solids dissolved, and then cooled to roomtemperature. A second solution was made by combining 3.57 grams ofVOSO₄.xH₂O (x=3 to 5) with 40 grams of deionized water. The firstsolution and second solution were combined and sufficient deionizedwater was added to bring the combined solution volume up to 82 mL toyield the molybdenum/vanadium impregnation solution. The support wasimpregnated with the molybdenum/vanadium impregnation solution and agedfor 2 hours with occasional agitation. The resulting support/metalmixture was heat-treated at 125° C. for several hours, and thenheat-treated at 480° C. for 2 hours. The resulting catalyst contained,per gram of catalyst, 0.02 grams of vanadium and 0.02 grams ofmolybdenum, with the balance being support.

Silicon carbide was positioned on top of the top contacting zone to filldead space and to serve as a preheat zone. The catalyst bed was loadedinto a Lindberg furnace that included four heating zones correspondingto the preheat zone, the top and bottom contacting zones, and the bottomsupport.

The catalysts were sulfided by introducing a gaseous mixture of 5 vol %hydrogen sulfide and 95 vol % hydrogen gas into the contacting zones ata rate of about 1.5 liter of gaseous mixture per volume (mL) of totalcatalyst (silicon carbide was not counted as part of the volume ofcatalyst) for the time periods set forth below. The reactor pressure wasabout 1.9 MPa (279.7 psi). Temperatures of the contacting zones wereincreased from ambient to 204° C. (400° F.) over 1 hour, and then heldat 204° C. for 2 hours. After holding at 204° C., the contacting zoneswere increased incrementally to 316° C. (600° F.) at a rate of about 10°C. (about 50° F.) per hour. The contacting zones were maintained at 316°C. for an hour, incrementally raised to 370° C. (700° F.) over 1 hour,and then held at 370° C. for two hours. The contacting zones were thenallowed to cool to ambient temperature.

After sulfiding, the contacting zones were then heated to 204° C. over 2hours and crude feed (BC-10, Brazil) was fed to the top of the reactor.The crude feed flowed through the preheat zone, top contacting zone,bottom contacting zone, and bottom support of the reactor. The crudefeed was contacted with each of the catalysts in the presence ofhydrogen gas. Contacting conditions were as follows: ratio of hydrogengas to the crude feed provided to the reactor was 656 Nm³/m³ (4000SCFB), LHSV was 0.5 h⁻¹, and pressure was 13.8 MPa (2014.7 psi). The twocontacting zones were incrementally heated from 204° C. to 390° C. at arate in a range from 0.1° C. per hour to 10° C. per hour, and thenmaintained at 390° C. for 311 hours. Temperatures of the catalyst bedwas incrementally raised to 400° C., and maintained at 400° C. for 352hours.

The total product (that is, the crude product and gas) exited thecatalyst bed. The total product was introduced into a gas-liquid phaseseparator. In the gas-liquid separator, the total product was separatedinto the crude product and gas. Gas input to the system was measured bya mass flow controller. Gas exiting the system was cooled to atemperature sufficient to remove any liquid components having a carbonnumber of at least 5 from the gas. The separated gas was measured usinga wet test meter. The crude product was periodically analyzed todetermine a weight percentage of components of the crude product. Crudeproduct and crude feed properties are summarized in Table 2. TABLE 2Crude Property Crude Feed Product TAN 3.6 ≦0.05 API Gravity 15.1 20Density at 15.56° C. (60° F.), 0.9651 0.9306 g/cm³ Hydrogen, wt % 11.412.1 Carbon, wt % 87.1 87.4 Sulfur, wt % 0.433 0.05 Oxygen, wt % 0.420.01 Nitrogen, wt % 0.52 0.24 Basic Nitrogen, wt % 0.16 0.08 Calcium,wtppm 3.5 0.6 Potassium, wtppm 1.8 1.3 Sodium, wtppm 5.3 0.6 Nickel,wtppm 12.4 7.3 Vanadium, wtppm 19.2 6.4 Iron, wtppm 10 0.4 Micro-CarbonResidue, wt % 8.5 4.6 C₅ Asphaltenes, wt % 7.5 4.3 Naphtha, wt % 0 4.1Distillate, wt % 17.5 26.6 VGO, wt % 39.2 40.9 Residue, wt % 43.3 28.4P-Value 5 3.6 Viscosity at 37.8° C. 1705 156 (100° F.), cSt

As shown in Table 2 the crude product had, per gram of crude product, anitrogen content of 0.0024 grams, a MCR content of 0.046 grams, and a C₅asphaltenes content of 0.043 grams. The crude product also had a calciumcontent of 0.6 wtppm, a potassium content of 1.3 wtppm, and a sodiumcontent of 0.6 wtppm.

Example 3 demonstrates that contacting the crude feed with one or morecatalysts at controlled contacting conditions produced a total productthat included the crude product. At least one of the catalysts was aColumn 6 metal catalyst that: (a) included Column 6 metal(s); (b) had apore size distribution with a median pore diameter of greater than 110Å; and (c) had a pore volume in which pores having a pore diameter of atleast 350 Å provided at most 10% of the pore volume. As measured byP-value, crude feed/total product mixture stability was maintained. Thecrude product had reduced MCR, a reduced alkali metal and alkaline-earthmetal salts in organic acids, reduced Ni/V/Fe content, reduced sulfurcontent, reduced nitrogen content, reduced C₅ asphaltenes, and reducedoxygen content relative to the crude feed.

Example 4 Preparation of a Catalyst Support

An alumina support was prepared by mulling 550 grams of alumina powder(Criterion Catalysts and Technologies LP), 26 grams of calcined aluminafines, 585 grams of water, and 8 grams of 16M nitric acid for 35minutes. The mulled mixture was extruded through 1.94 mm and 3.28 mmdiameter die plates, heat-treated at 93° C. (200° F.), 107° C. (225°F.), and then heat-treated at 121° C. (250° F.) until a loss on ignitionin a range of 27 wt % to 30 wt %, based on initial extrudate weight, wasobtained. Loss on ignition was performed as described in Example 1. Theextrudates were further heat-treated at 918° C. (1685° F.) for 1 hour.The support had an average pore diameter of 186.4 Å, a pore volume of0.868 cm³/mL, and pores with a diameter of at least 350 Å, whichprovided 13.3% of the total pore volume of the support. Example 4demonstrates preparation of a support that has an average pore diameterof at least 90 Å and a pore volume in which pores having a pore diameterof at least 350 Å provide at most 15% of the pore volume of the support.

Example 5 Preparation of a Catalyst having a Median Pore Diameter of 250Å and a Selected Pore Volume Distribution

The alumina support prepared as described in Example 4 was impregnatedwith a molybdenum/cobalt/phosphorus impregnation solution prepared asfollows. MoO₃ (22.95 grams) was combined with 85 wt % H₃PO₄ (12.67grams), and heated to 82° C. (180° F.) to form a molybdenum/phosphoroussolution. Co(OH)₂ (29.83 grams) was added to the molybdenum/phosphorussolution and the resulting molybdenum/cobalt/phosphorus solution washeated to 100° C. Citric acid monohydrate (21.5 grams) was added to themolybdenum/cobalt/phosphorus solution, heated to 100° C., and maintainedat 100° C. for 1 hour. The resulting solution was reduced in volume to252 mL to produce the molybdenum/cobalt/phosphorus impregnationsolution. The impregnation solution had a pH of 3.22.

The alumina support (300.0 grams) was combined with the impregnationsolution and aged for several hours with occasional agitation. Theresulting support/metal mixture was heat-treated at 120° C. for severalhours, and then heat-treated at 426° C. (800° F.) for 2 hours. Theresulting catalyst was further heat-treated at 593° C. (1100° F.) for 2hours. The catalyst contained, per gram of catalyst, 0.153 grams ofmolybdenum, 0.043 grams of cobalt, and 0.008 grams of phosphorus, withthe balance being support. The catalyst had a pore size distributionwith a median pore diameter of 250 Å, with 67% of the total number ofpores having a pore diameter within 58 Å of the median pore diameter.The surface area of the catalyst was 98 m²/g. The pore volumedistribution is summarized in Table 3. TABLE 3 % of pore volume Range, ÅCatalyst  <70 0  70-100 0 100-130 0.15 130-150 0.5 150-180 2.5 180-2004.25 200-240 22.66 240-300 63.77 300-350 3.36 350-450 0.98 450-600 0.46 600-1000 0.44 1000-3000 0.46 3000-5000 0.46 >5000 0

As shown in Table 3, pores having a pore diameter of at least 350 Åprovided 2.8% of the total pore volume of the catalyst.

Example 5 demonstrates the preparation of the Column 6 metal catalysthaving a pore size distribution with a median pore diameter of greaterthan 110 Å, and a pore volume in which pores of at least 350 Å provideat most 10% of the total pore volume. This example also demonstrates thepreparation of the Column 6 metal catalyst from a support having anaverage pore diameter of at least 90 Å, and a pore volume in which poreshaving a pore diameter of at least 350 Å provide at least 15% of thetotal pore volume.

Example 6 Contact of a Crude Feed with Two Catalysts

The reactor apparatus (except for content of contacting zones), thecrude feed, catalyst sulfiding method, total product separation method,contacting conditions, contacting time, and crude product analysis werethe same as described in Example 3.

The crude feed flowed from the top of the reactor to the bottom of thereactor. A molybdenum/cobalt/phosphorus catalyst prepared as describedin Example 5 was mixed with silicon carbide and the mixture (81 cm³) waspositioned in the bottom contacting zone. The molybdenum/vanadiumcatalyst on a theta alumina support, prepared as described in Example 3was mixed with silicon carbide. The molybdenum-vanadium catalyst/siliconcarbide mixture (9 cm³) was positioned in the top contacting zone.

Crude product properties are summarized in Table 4. TABLE 4 CrudeProperty Crude Feed Product TAN 3.6 ≦0.05 API Gravity 15.1 19.2 Densityat 15.56° C. 0.9651 0.9554 (60° F.), g/cm³ Hydrogen, wt % 11.4 11.6Carbon, wt % 87.1 87.6 Sulfur, wt % 0.43 0.16 Oxygen, wt % 0.42 0.11Nitrogen, wt % 0.52 0.47 Calcium, wtppm 5.4 0.5 Potassium, wtppm 46 1.5Sodium, wtppm 117 0.6 Nickel, wtppm 12.4 7.5 Vanadium, wtppm 19.2 6.2Iron, wtppm 10.4 0.9 Micro-Carbon Residue, wt % 8.5 7.2 C₅ Asphaltenes,wt % 7.5 5.0 Naphtha, wt % 0 2.3 Distillate, wt % 17.5 20.3 VGO, wt %39.2 42.0 Residue, wt % 43.3 35.4 P-Value 5 4.2 Viscosity at 37.8° C.1705 698 (100° F.), cSt

As shown in Table 4, the crude product had a nitrogen content of 0.0047grams, a MCR content of 0.072 grams and a C₅ asphaltenes content of 0.05grams, per gram of crude product. The crude product also had 0.5 wtppmof calcium, 1.5 wtppm of potassium, and 0.6 wtppm of sodium.

Example 6 demonstrates that contacting the crude feed with one or morecatalysts under controlled contacting conditions produced a totalproduct that included the crude product. At least one of the catalystswas a Columns 6 metal catalyst that: (a) included Column 6 metal(s); (b)had a pore size distribution with a median pore diameter of greater than110 Å; and (c) had a pore volume in which pores having a pore diameterof at least 350 Å provided at most 10% of the pore volume. The crudeproduct had reduced MCR, reduced alkali metal and alkaline-earth metalsalts of organic acids, reduced Ni/V/Fe content, reduced sulfur content,reduced nitrogen content, reduced C₅ asphaltenes, and reduced oxygencontent relative to the crude feed.

In this patent, certain U.S. patents and U.S. patent applications havebeen incorporated by reference. The text of such U.S. patents and U.S.patent applications is, however, only incorporated by reference to theextent that no conflict exists between such text and the otherstatements and drawings set forth herein. In the event of such conflict,then any such conflicting text in such incorporated by reference U.S.patents and U.S. patent applications is specifically not incorporated byreference in this patent.

Further modifications and alternative embodiments of various aspects ofthe invention will be apparent to those skilled in the art in view ofthis description. Accordingly, this description is to be construed asillustrative only and is for the purpose of teaching those skilled inthe art the general manner of carrying out the invention. It is to beunderstood that the forms of the invention shown and described hereinare to be taken as examples of embodiments. Elements and materials maybe substituted for those illustrated and described herein, parts andprocesses may be reversed and certain features of the invention may beutilized independently, all as would be apparent to one skilled in theart after having the benefit of this description of the invention.Changes may be made in the elements described herein without departingfrom the spirit and scope of the invention as described in the followingclaims.

1. A method of producing a crude product, comprising: contacting a crudefeed with one or more catalysts to produce a total product that includesthe crude product, wherein the crude product is a liquid mixture at 25°C. and 0.101 MPa; the crude feed has a nitrogen content of at least0.0001 grams per gram of crude feed; and at least one of the catalystsis a Column 6 metal catalyst that comprises: one or more metals fromColumn 6 of the Periodic Table and/or one or more compounds of one ormore metals from Column 6 of the Periodic Table; a pore sizedistribution with a median pore diameter of greater than 110 Å; and apore volume in which pores having a pore diameter of at least 350 Åprovide at most 10% of the pore volume, wherein pore diameter and porevolume are as determined by ASTM Method D4282; and controllingcontacting conditions such that the crude product has a nitrogen contentof at most 90% of the nitrogen content of the crude feed, whereinnitrogen content is as determined by ASTM Method D5762.
 2. The method asclaimed in claim 1, wherein pores having a pore diameter of at least 350Å provide at most 5% of the pore volume.
 3. The method as claimed inclaims 1, wherein the nitrogen content of the crude product is at most50% of the nitrogen content of the crude feed.
 4. The method as claimedin claim 1, wherein the nitrogen content of the crude product is in arange from 0.1% to 75% of the nitrogen content of the crude feed.
 5. Themethod as claimed in claim 1, wherein the crude feed has from 0.0001grams to 0.1 grams, 0.001 grams to 0.05 grams of nitrogen per gram ofcrude feed.
 6. The method as claimed in claim 1, wherein the crudeproduct has from 0.00001 grams to 0.05 grams of nitrogen per gram ofcrude product.
 7. The method as claimed in claim 1, wherein the Column 6metal catalyst has, per gram of catalyst, from 0.0001 grams to 0.3 gramsof one or more of the Column 6 metals and/or one or more of the Column 6metal compounds, calculated as total weight of Column 6 metal.
 8. Themethod as claimed in claim 1, wherein the Column 6 metal catalystcomprises in addition one or more metals from Columns 7-10 of thePeriodic Table and/or one or more compounds of one or more metals fromColumns 7-10 of the Periodic Table.
 9. The method as claimed in claim 8,wherein the Column 6 metal catalyst has, per gram of catalyst, from0.001 grams to 0.1 grams of one or more of the Columns 7-10 metalsand/or one or more of the Columns 7-10 metal compounds, calculated astotal weight of Columns 7-10 metals.
 10. The method as claimed in claim1, wherein the Column 6 metal catalyst comprises in addition one or moremetals from Column 10 of the Periodic Table and/or one or more compoundsof one or more metals from Column 10 of the Periodic Table.
 11. Themethod as claimed in claim 1, wherein the Column 6 metal catalystcomprises molybdenum and/or tungsten.
 12. The method as claimed in claim11, wherein the Column 6 metal catalyst comprises nickel.
 13. The methodas claimed in claim 11, wherein the Column 6 metal catalyst comprisesnickel and iron.
 14. The method as claimed in claim 13, wherein a molarratio of total molybdenum to total nickel and iron is at least 1.5. 15.The method as claimed in claim 1, wherein the Column 6 metal catalystcomprises in addition one or more elements from Column 15 of thePeriodic Table and/or one or more compounds of one or more elements fromColumn 15 of the Periodic Table.
 16. The method as claimed in claim 15,wherein the catalyst has, per gram of catalyst, from 0.000001 grams to0.1 grams of one or more of the Column 15 elements and/or one or more ofthe Column 15 element compounds, calculated as total weight of Column 15element.
 17. The method as claimed in claim 1, wherein the Column 6metal catalyst comprises in addition phosphorus.
 18. The method asclaimed in claim 1, wherein the Column 6 metal catalyst has, per gram ofcatalyst, from 0.001 grams to 0.15 grams of molybdenum and/or one ormore compounds of molybdenum, calculated as total weight of molybdenum;and from 0.001 grams to 0.05 grams of nickel and/or one or morecompounds of nickel, calculated as total weight of nickel.
 19. Themethod as claimed in claim 18, wherein the Column 6 metal catalyst hasin addition, per gram of catalyst, from 0.001 grams to 0.05 grams ofphosphorus and/or one or more compounds of phosphorus, calculated astotal weight of phosphorus.
 20. The method as claimed in claim 19,wherein the Column 6 metal catalyst has in addition, per gram ofcatalyst, from 0.001 grams to 0.05 grams of iron and/or one or morecompounds of iron, calculated as total weight of iron.
 21. The method asclaimed in claim 1, wherein the Column 6 metal catalyst has at most0.001 grams per gram of catalyst of one or more metals from Column 5 ofthe Periodic Table and/or one or more compounds of one or more metalsfrom Column 5 of the Periodic Table, calculated as total weight ofColumn 5 metal.
 22. The method as claimed in claim 1, wherein the Column6 metal catalyst has a median pore diameter of at least 120 Å or at most300 Å, wherein pore size distribution is as determined by ASTM MethodD4282.
 23. The method as claimed in claim 1, wherein the Column 6 metalcatalyst has a pore size distribution such that at least 60% of thetotal number of pores in the pore size distribution are within 45 Å ofthe median pore diameter of the pore size distribution.
 24. The methodas claimed in claim 1, wherein the Column 6 metal catalyst comprises inaddition a support, and the support has, per gram of support, at least0.8 grams of gamma alumina.
 25. The method as claimed in claim 24,wherein the support has, per gram of support, at most 0.1 grams ofsilica.
 26. The method as claimed in claim 1, wherein the Column 6 metalcatalyst is obtainable by combining a mixture with one or more of theColumn 6 metals and/or one or more of the Column 6 metal compounds, andthe mixture comprises: one or more metals from Columns 7-10 of thePeriodic Table and/or one or more compounds of one or more metals fromColumns 7-10 of the Periodic Table; and a support.
 27. The method asclaimed in claim 26, wherein at least one of the Columns 7-10 metalscomprises nickel, cobalt, iron, or mixtures thereof.
 28. The method asclaimed in claim 1, wherein crude feed also has a C₅ asphaltenescontent, and the crude product has a C₅ asphaltenes content of at most90% of the C₅ asphaltenes content of the crude feed, wherein C₅asphaltenes content is as determined by ASTM Method D2007.
 29. Themethod as claimed in claim 1, wherein the crude product has a viscosityat 37.8° C. (100° F.) of at most 90% of the viscosity at 37.8° C. of thecrude feed, wherein viscosity is as determined by ASTM Method D445. 30.The method as claimed in claim 1, wherein the crude feed also has asulfur content, and the crude product has a sulfur content of at most90% of the sulfur content of the crude feed, wherein sulfur content isas determined by ASTM Method D4294.
 31. The method as claimed in claim1, wherein the crude feed also has a residue content, and the crudeproduct has a residue content of at most 90% of the residue content ofthe crude feed, wherein residue content is as determined by ASTM MethodD5307.
 32. The method as claimed in claim 1, wherein the contacting isperformed in the presence of a hydrogen source.
 33. The method asclaimed in claim 1, wherein the contacting conditions comprise: atemperature within the range of 50° C. to 500° C.; a total pressurewithin a range of 0.1 MPa to 20 MPa; a liquid hourly space velocity ofat least 0.05 h⁻¹; and a ratio of a gaseous hydrogen source to the crudefeed in a range from 0.1 Nm³/m³ to 100,000 Nm³/m³.
 34. The method asclaimed in claim 33, wherein the total pressure is at most 18 MPa. 35.The method as claimed in claim 33, wherein the temperature is at most430° C.
 36. The method as claimed in claim 1, wherein a crude feed/totalproduct mixture has a P-value of at least 1.5 during contacting.
 37. Themethod as claimed in claim 1, wherein the method further comprisescombining the crude product with a crude that is the same as ordifferent from the crude feed to form a blend.
 38. The method of claim 1or claim 37 further comprising the step of processing the crude productor blend to produce transportation fuel, heating fuel, lubricants, orchemicals.